Semiconductor device and method for manufacturing the same

ABSTRACT

A semiconductor device includes a semiconductor substrate, a first insulating film formed on the semiconductor substrate, a charge storage layer formed on the first insulating film, a second insulating film formed on the charge storage layer, and a control electrode formed on the second insulating film, the second insulating film including a lower silicon nitride film, a lower silicon oxide film formed on the lower silicon nitride film, an intermediate insulating film formed on the lower silicon oxide film and containing a metal element, the intermediate insulating film having a relative dielectric constant of greater than 7, an upper silicon oxide film formed on the intermediate insulating film, and an upper silicon nitride film formed on the upper silicon oxide film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromprior Japanese Patent Applications No. 2006-112192, filed Apr. 14, 2006;and No. 2007-037153, filed Feb. 16, 2007, the entire contents of both ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device and a method formanufacturing the semiconductor device.

2. Description of the Related Art

For nonvolatile semiconductor memory devices, a proposal has been madethat a high dielectric constant insulating film be provided between acontrol electrode and a charge storage layer in order to increase thecapacitance between the control electrode and the charge storage layer(see, for example, Jpn. Pat. Appln. KOKAI Publication No. 5-129625).

However, sufficient examinations have not been made for the insulatingfilm provided between the control electrode and the charge storagelayer. It has thus been difficult to obtain a nonvolatile semiconductormemory device offering excellent characteristics and improvedreliability.

BRIEF SUMMARY OF THE INVENTION

A semiconductor device in accordance with a first aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film including a lower silicon nitride film,a lower silicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film.

A semiconductor device in accordance with a second aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structure, asecond film structure, and a third film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, the third film structure including alower silicon nitride film, an intermediate insulating film formed onthe lower silicon nitride film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, and an upper silicon nitride film formed on theintermediate insulating film, the intermediate insulating film having athickness equal to or greater than that of one atomic layer and equal toor smaller than 5 nm.

A semiconductor device in accordance with a third aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structureand a second film structure, the first film structure including a lowersilicon oxide film, an intermediate insulating film formed on the lowersilicon oxide film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon oxide film formed on the intermediate insulatingfilm, the second film structure including a lower silicon nitride film,a lower silicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, the intermediateinsulating film being formed of a polycrystalline film, and crystalgrains contained in the polycrystalline film having an average grainsize of at least 5 nm.

A semiconductor device in accordance with a fourth aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structure, asecond film structure, and a third film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, the third film structure including alower silicon nitride film, an intermediate insulating film formed onthe lower silicon nitride film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, and an upper silicon nitride film formed on theintermediate insulating film, wherein the following expression issatisfied, T/(T+M+S)≧0.2, where T (T>0) is a concentration of atransition metal element in the intermediate insulating film, M (M≧0) isa concentration of a metal element other than the transition metalelement in the intermediate insulating film, and S (S≧0) is aconcentration of a semiconductor element in the intermediate insulatingfilm.

A semiconductor device in accordance with a fifth aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structure, asecond film structure, and a third film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, the third film structure including alower silicon nitride film, an intermediate insulating film formed onthe lower silicon nitride film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, and an upper silicon nitride film formed on theintermediate insulating film, the intermediate insulating film having acarbon concentration of at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³.

A semiconductor device in accordance with a sixth aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structure, asecond film structure, and a third film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, the third film structure including alower silicon nitride film, an intermediate insulating film formed onthe lower silicon nitride film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, and an upper silicon nitride film formed on theintermediate insulating film, the intermediate insulating film having anitrogen concentration of at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³.

A semiconductor device in accordance with a seventh aspect of thepresent invention comprises: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure, a second film structure, and a third filmstructure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, the third filmstructure including a lower silicon nitride film, an intermediateinsulating film formed on the lower silicon nitride film and containinga metal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon nitride filmformed on the intermediate insulating film, the intermediate insulatingfilm having a hydrogen concentration of at least 1×10¹⁹ atoms/cm³ and atmost 5×10²² atoms/cm³.

A semiconductor device in accordance with an eighth aspect of thepresent invention comprises: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure and a second film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, at least one of the lower silicon oxidefilm and the upper silicon oxide film being thicker than theintermediate insulating film.

A semiconductor device in accordance with a ninth aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structureand a second film structure, the first film structure including a lowersilicon oxide film, an intermediate insulating film formed on the lowersilicon oxide film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon oxide film formed on the intermediate insulatingfilm, the second film structure including a lower silicon nitride film,a lower silicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, at least one of thelower silicon oxide film and the upper silicon oxide film having acarbon concentration of at least 1×10¹⁹ atoms/cm³.

A semiconductor device in accordance with a tenth aspect of the presentinvention comprises: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structureand a second film structure, the first film structure including a lowersilicon oxide film, an intermediate insulating film formed on the lowersilicon oxide film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon oxide film formed on the intermediate insulatingfilm, the second film structure including a lower silicon nitride film,a lower silicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, at least one of thelower silicon oxide film and the upper silicon oxide film having achlorine concentration of at least 1×10¹⁹ atoms/cm³.

A semiconductor device in accordance with a eleventh aspect of thepresent invention has a plurality of memory cells each comprising: afirst insulating film formed on a semiconductor substrate; a chargestorage layer formed on the first insulating film; a second insulatingfilm formed on the charge storage layer; and a control electrode formedon the second insulating film, the second insulating film including ahigh dielectric constant insulating film containing a metal element andhaving a relative dielectric constant of greater than 7, the highdielectric constant insulating film having a first part formed along atop surface of the charge storage layer, a second part formed along aside surface of the charge storage layer, and a third part formedbetween the adjacent charge storage layers, the third part having alower oxygen concentration than the first part.

A method for manufacturing a semiconductor device in accordance with atwelfth aspect of the present invention comprises: forming a firstinsulating film on a semiconductor substrate; forming a charge storagelayer on the first insulating film; forming a second insulating film onthe charge storage layer; and forming a control electrode film on thesecond insulating film, forming the second insulating film including oneof forming a first film structure, forming a second film structure, andforming a third film structure, forming the first film structureincluding forming a lower silicon oxide film, forming an intermediateinsulating film on the lower silicon oxide film, the intermediateinsulating film containing a metal element and oxygen and having arelative dielectric constant of greater than 7, and forming an uppersilicon oxide film on the intermediate insulating film; forming thesecond film structure including forming a lower silicon nitride film,forming a lower silicon oxide film on the lower silicon nitride film,forming an intermediate insulating film on the lower silicon oxide film,the intermediate insulating film containing a metal element and oxygenand having a relative dielectric constant of greater than 7, forming anupper silicon oxide film on the intermediate insulating film, andforming an upper silicon nitride film on the upper silicon oxide film;forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and oxygen and having a relative dielectric constant ofgreater than 7, and forming an upper silicon nitride film on theintermediate insulating film, the intermediate insulating film beingformed by CVD or ALD using ozone or oxygen radicals as an oxygen source.

A method for manufacturing a semiconductor device in accordance with athirteenth aspect of the present invention comprises: forming a firstinsulating film on a semiconductor substrate; forming a charge storagelayer on the first insulating film; forming a second insulating film onthe charge storage layer; and forming a control electrode film on thesecond insulating film, forming the second insulating film including oneof forming a first film structure, forming a second film structure, andforming a third film structure, forming the first film structureincluding forming a lower silicon oxide film, forming an intermediateinsulating film on the lower silicon oxide film, the intermediateinsulating film containing a metal element and oxygen and having arelative dielectric constant of greater than 7, and forming an uppersilicon oxide film on the intermediate insulating film; forming thesecond film structure including forming a lower silicon nitride film,forming a lower silicon oxide film on the lower silicon nitride film,forming an intermediate insulating film on the lower silicon oxide film,the intermediate insulating film containing a metal element and oxygenand having a relative dielectric constant of greater than 7, forming anupper silicon oxide film on the intermediate insulating film, andforming an upper silicon nitride film on the upper silicon oxide film;forming the third film structure including forming a lower siliconnitride, forming an intermediate insulating film on the lower siliconnitride film, the intermediate insulating film containing a metalelement and oxygen and having a relative dielectric constant of greaterthan 7, and forming an upper silicon nitride film on the intermediateinsulating film, the intermediate insulating film being formed by CVD orALD using water vapor as an oxygen source.

A method for manufacturing a semiconductor device in accordance with afourteenth aspect of the present invention comprises: forming a firstinsulating film on a semiconductor substrate; forming a charge storagelayer on the first insulating film; forming a second insulating film onthe charge storage layer; and forming a control electrode film on thesecond insulating film, forming the second insulating film including oneof forming a first film structure, forming a second film structure, andforming a third film structure, forming the first film structureincluding forming a lower silicon oxide film, forming an intermediateinsulating film on the lower silicon oxide film, the intermediateinsulating film containing a metal element and oxygen and having arelative dielectric constant of greater than 7, and forming an uppersilicon oxide film on the intermediate insulating film; forming thesecond film structure including forming a lower silicon nitride film,forming a lower silicon oxide film on the lower silicon nitride film,forming an intermediate insulating film on the lower silicon oxide film,the intermediate insulating film containing a metal element and oxygenand having a relative dielectric constant of greater than 7, forming anupper silicon oxide film on the intermediate insulating film, andforming an upper silicon nitride film on the upper silicon oxide film;forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and oxygen and having a relative dielectric constant ofgreater than 7, and forming an upper silicon nitride film on theintermediate insulating film, forming the second insulating filmincluding, after forming the intermediate insulating film, performing aheat treatment at a temperature higher than that at which theintermediate insulating film is formed.

A method for manufacturing a semiconductor device in accordance with afifteenth aspect of the present invention comprises: forming a firstinsulating film on a semiconductor substrate; forming a charge storagelayer on the first insulating film; forming a second insulating film onthe charge storage layer; and forming a control electrode film on thesecond insulating film, forming the second insulating film including oneof forming a second film structure, and forming a third film structure,forming the second film structure including forming a lower siliconnitride film, forming a lower silicon oxide film on the lower siliconnitride film, forming an intermediate insulating film on the lowersilicon oxide film, the intermediate insulating film containing a metalelement and having a relative dielectric constant of greater than 7,forming an upper silicon oxide film on the intermediate insulating film,and forming an upper silicon nitride film on the upper silicon oxidefilm; forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and having a relative dielectric constant of greater than7, and forming an upper silicon nitride film on the intermediateinsulating film, forming the second insulating film including, afterforming the lower silicon nitride film, performing a heat treatment at atemperature higher than that at which the lower silicon nitride film isformed.

A method for manufacturing a semiconductor device in accordance with asixteenth aspect of the present invention comprises: forming a firstinsulating film on a semiconductor substrate; forming a charge storagelayer on the first insulating film; forming a second insulating film onthe charge storage layer; and forming a control electrode film on thesecond insulating film, forming the second insulating film includingforming a silicon nitride film on the charge storage layer, forming thesilicon nitride film including forming a silicon layer on the chargestorage layer and nitriding the silicon layer.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIGS. 1A and 1B are sectional views schematically showing a part of abasic process of manufacturing a semiconductor device in accordance withembodiments of the present invention;

FIGS. 2A and 2B are sectional views schematically showing a part of thebasic process of manufacturing a semiconductor device in accordance withthe embodiments of the present invention;

FIGS. 3A and 3B are sectional views schematically showing a part of thebasic process of manufacturing a semiconductor device in accordance withthe embodiments of the present invention;

FIGS. 4A and 4B are sectional views schematically showing a part of thebasic process of manufacturing a semiconductor device in accordance withthe embodiments of the present invention;

FIGS. 5A and 5B are sectional views schematically showing a part of thebasic process of manufacturing a semiconductor device in accordance withthe embodiments of the present invention;

FIGS. 6A and 6B are sectional views schematically showing the detailedconfiguration of a semiconductor device in accordance with a firstembodiment of the present invention;

FIG. 7 is a diagram showing the relationship between a film thicknessratio (film thickness of a silicon oxide film/film thickness of a highdielectric constant insulating film) and a leakage current in accordancewith the first embodiment of the present invention;

FIG. 8 is a diagram showing the relationship between the concentrationof a transition metal element and the thickness of an interface layer;

FIG. 9 is a diagram showing the relationship between the average grainsize of crystal grains contained in the high dielectric constantinsulating film and a leakage current in accordance with the firstembodiment of the present invention;

FIG. 10 is a diagram showing the relationship between the number ofcycles for the growth of an atomic layer in the high dielectric constantinsulating film and the leakage current in accordance with the firstembodiment of the present invention;

FIG. 11 is a diagram showing the relationship between the film thicknessof the high dielectric constant insulating film and the leakage currentin accordance with the first embodiment of the present invention;

FIGS. 12A and 12B are sectional views schematically showing a part of aprocess of manufacturing a semiconductor device in accordance with thefirst embodiment of the present invention in detail;

FIG. 13 is a sectional view schematically showing the detailedconfiguration of a semiconductor device in accordance with a secondembodiment of the present invention;

FIGS. 14A and 14B are sectional views schematically showing a part of aprocess of manufacturing a semiconductor device in accordance with thesecond embodiment of the present invention in detail;

FIG. 15 is a sectional view schematically showing the detailedconfiguration of a semiconductor device in accordance with a thirdembodiment of the present invention;

FIGS. 16A and 16B are sectional views showing a part of a process ofmanufacturing a semiconductor device in accordance with the thirdembodiment of the present invention in detail;

FIG. 17 is a diagram showing the relationship between the concentrationof carbon in the high dielectric constant insulating film and a leakagecurrent density in accordance with a fourth embodiment of the presentinvention;

FIG. 18 is a diagram showing the relationship between the concentrationof carbon in the high dielectric constant insulating film and an etchingrate in accordance with the fourth embodiment of the present invention;

FIG. 19 is a diagram showing the relationship between the concentrationof nitrogen in the high dielectric constant insulating film and theleakage current density in accordance with a fifth embodiment of thepresent invention;

FIG. 20 is a diagram showing the distribution of concentration ofaluminium in a depth direction in accordance with the fifth embodimentof the present invention;

FIG. 21 is a diagram showing the relationship between the concentrationof hydrogen in the high dielectric constant insulating film and theleakage current density in accordance with a sixth embodiment of thepresent invention;

FIG. 22 is a diagram showing measurements of electric capacitance inaccordance with the sixth embodiment of the present invention;

FIG. 23 is a sectional view schematically showing the detailedconfiguration of a semiconductor device in accordance with an eighthembodiment of the present invention;

FIG. 24 is a sectional view showing a part of a process of manufacturinga semiconductor device in accordance with the eighth embodiment of thepresent invention in detail;

FIG. 25 is a diagram showing the relationship between the concentrationof chlorine in a silicon oxide film and the yield of a tunnel insulatingfilm in accordance with a ninth embodiment of the present invention;

FIG. 26 is a diagram showing the relationship between the concentrationof carbon in the silicon oxide film and the amount of variation inthreshold (VTh) caused by detrapping in accordance with a ninthembodiment of the present invention;

FIG. 27 is a sectional view schematically showing the basicconfiguration of a semiconductor device in accordance with a tenthembodiment of the present invention;

FIG. 28 is a diagram showing the amount of fixed charge in a memory cellwhen ozone or steam is used as an oxygen source for the high dielectricconstant insulating film in accordance with the first embodiment of thepresent invention;

FIG. 29 is a diagram showing the relationship between the temperature atwhich an aluminium oxide film is formed and an etching amount inaccordance with the first embodiment of the present invention;

FIG. 30 is a diagram showing the relationship between the temperature atwhich an aluminium oxide film is formed and a Vfb shift in memory cellsin accordance with the first embodiment of the present invention;

FIG. 31 is a diagram showing the relationship between a temperature forheat treatment after formation of an aluminium oxide film and theetching amount in accordance with the first embodiment of the presentinvention;

FIG. 32 is a diagram showing the effects of the heat treatment inaccordance with the third embodiment of the present invention;

FIG. 33 is a diagram showing the relationship between the heat treatmenttemperature and a low electric field leakage current in accordance withthe third embodiment of the present invention;

FIG. 34 is a sectional view schematically showing a part of a process ofmanufacturing a semiconductor device in accordance with an eleventhembodiment of the present invention;

FIG. 35 is a sectional view schematically showing a part of the processof manufacturing a semiconductor device in accordance with the eleventhembodiment of the present invention;

FIGS. 36A, 36B, and 36C are diagrams showing the programmingcharacteristic of memory cells in accordance with the eleventhembodiment of the present invention;

FIG. 37 is a sectional view schematically showing a part of the processof manufacturing a semiconductor device in accordance with a twelfthembodiment of the present invention;

FIG. 38 is a diagram showing the relationship between the temperature atwhich a silicon nitride film is formed and the concentration of hydrogenin an isolation insulating film in accordance with the twelfthembodiment of the present invention; and

FIG. 39 is a diagram showing the relationship between the temperature atwhich the silicon nitride film is formed and a leakage current of aninter-electrode insulating film in accordance with the twelfthembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described below withreference to the drawings.

Embodiment 1

With reference to FIGS. 1A and 1B to 5A and 5B, description will begiven of a basic method for manufacturing a semiconductor device(nonvolatile semiconductor memory device) in accordance with the presentembodiment. FIGS. 1A to 5A are sectional views in a bit line direction(channel length directions). FIGS. 1B to 5B are sectional views in aword line direction (channel width direction).

First, as shown in FIGS. 1A and 1B, a tunnel insulating film (firstinsulating film) 12 of thickness 6 nm is formed on a surface of asilicon substrate (semiconductor substrate) 11 doped with impurities bypyrolysis oxidation. A phosphorus-doped polycrystalline silicon film ofthickness 100 nm is subsequently formed by CVD (Chemical VaporDeposition) as a floating gate electrode film 13. Moreover, a mask film14 is formed by CVD.

Then, the mask film 14, polycrystalline silicon film 13, tunnelinsulating film 12, and silicon substrate 11 are sequentially etched byRIE (Reactive Ion Etching) through a first resist mask (not shown) as amask. This forms an element formation area 15 and an isolation trench16. Both the element formation area 15 and the isolation trench 16 havea width of about 50 nm.

Then, as shown in FIGS. 2A and 2B, a silicon oxide film is formed on themask film 14 and in the isolation trench 16 as an isolation insulatingfilm 17. The silicon oxide film 17 on the mask film 14 is removed by CMP(Chemical Mechanical Polishing), with the silicon oxide film 17 in theisolation trench 16 left.

Then, as shown in FIGS. 3A and 3B, the mask film 14 is etched away witha chemical or the like to expose a top surface of the polycrystallinesilicon film 13. An upper part of the silicon oxide film 17 is etchedaway with a diluted fluorinated acid solution to expose the upper partof side surfaces of the polycrystalline silicon film 13. The exposedside surfaces have a height of about 50 nm.

Then, as shown in FIGS. 4A and 4B, an inter-electrode insulating film(second insulating film) 20 is formed all over the surface of theresulting structure. The inter-electrode insulating film 20 will bedescribed below in detail. Subsequently, a control gate electrode film21 of thickness 100 nm is formed on the inter-electrode insulating film20. The control gate electrode film 21 has a stack structure includingthe polycrystalline silicon film and a tungsten silicide film. A siliconnitride film is deposited by CVD as a mask film 22 for RIE.

Then, a second resist mask (not shown) having a pattern orthogonal tothe pattern of the first resist mask is formed on the silicon nitridefilm 22. The mask film 22, control gate electrode film 21,inter-electrode insulating film 20, polycrystalline silicon film 13, andtunnel insulating film 12 are sequentially etched by RIE through thesecond resist mask as a mask. This forms a floating gate electrode(charge storage layer) 13 and a control gate electrode (controlelectrode) 21. The width of the floating gate electrode 13 and thedistance between the floating gate electrodes 13 are both about 50 nm.

Then, as shown in FIGS. 5A and 5B, a gate sidewall film 23 of thicknessabout 10 nm is formed by thermal oxidation or CVD so as to cover thegate structure obtained in the steps shown in FIGS. 4A and 4B. Animpurity diffusion layer 24 constituting a source/drain area is formedby ion implantation and thermal annealing. An interlayer insulating film25 is formed by CVD. Wiring and the like (not shown) are further formedusing a well-known technique.

As described above, a nonvolatile semiconductor memory device isobtained which comprises the silicon substrate (semiconductor substrate)11, the tunnel insulating film (first insulating film; electriccapacitance C1) 12 formed on the silicon substrate 11, the floating gateelectrode (charge storage layer) 13 formed on the tunnel insulating film12, the inter-electrode insulating film (second insulating film;electric capacitance C2) 20 formed on the floating gate electrode 13,the control gate electrode (control electrode) 21 formed on theinter-electrode insulating film 20, and the impurity diffusion layers 24sandwiching a channel area under the floating gate electrode 13.

In each memory cell in the nonvolatile semiconductor memory device thusobtained, a high voltage is applied to between the silicon substrate 11and the control gate electrode 21 to apply an electric fieldcorresponding to a coupling ratio (C2/(C1+C2)) to the tunnel insulatingfilm 12. This allows a tunnel current to pass through the tunnelinsulating film 12. This changes the amount of charge stored in thefloating gate electrode 13 and thus a threshold for the memory cell toperform a data programming or erasing operation.

In an actual nonvolatile semiconductor memory device, a plurality ofmemory cells are arranged in a word like direction and a bit linedirection. A typical example of the above nonvolatile semiconductormemory device is a NAND type nonvolatile memory having a plurality ofseries connected memory cells between select transistors.

The above description relates to the basic configuration of and thebasic manufacturing method for the nonvolatile semiconductor memorydevice. The above basic configuration of and the basic manufacturingmethod for the nonvolatile semiconductor memory device are alsoapplicable to other embodiments.

FIGS. 6A and 6B are sectional views schematically showing the detailedconfiguration of the nonvolatile semiconductor memory device inaccordance with the present embodiment. FIG. 6A is a sectional view inthe word line direction (channel width direction). FIG. 6B is asectional view in the bit line direction (channel length direction).Components corresponding to those shown in FIGS. 1A and 1B to 5A and 5Bare denoted by the same reference numerals with their detaileddescription omitted.

As shown in FIGS. 6A and 6B, the inter-electrode insulating film 20 isformed of a stack film including a lower silicon oxide film 201, a highdielectric constant insulting film (intermediate insulating film) 202formed on the lower silicon oxide film 201, and an upper silicon oxidefilm 203 formed on the high dielectric constant insulating film 202. Thehigh dielectric constant insulating film 202 contains at least a metalelement and has a relative dielectric constant greater than 7. That is,the high dielectric constant insulating film 202 has a relativedielectric constant greater than that (about 7) of a typical siliconnitride film (Si₃N₄). The high dielectric constant insulating film 202preferably contains oxygen in addition to a metal element.

As described above, the inter-electrode insulating film 20 has the stackstructure including the lower silicon oxide film 201, high dielectricconstant insulating film 202, and upper silicon oxide film 203. Thisenables a sharp reduction in a leakage current of the inter-electrodeinsulating film 20 when a low electric field of at most about 10 MV/cmis applied. This enables a sufficient memory retention characteristic tobe offered. Further, the amount of charge trapped is sharply reduced,and trapped charge is unlikely to be discharged. This makes it possibleto avoid memory malfunctions resulting from a variation in the thresholdfor the memory cell. Moreover, a breakdown voltage significantlyincreases, enabling the realization of a sufficient memory operationspeed.

By providing the silicon oxide films 201 and 203 having a larger barrierheight than the high dielectric constant insulating film 202, it ispossible to reduce the leakage current generated when a low electricfield is applied to the inter-electrode insulating film 20 for memoryretention or the like. The lower silicon oxide film 201 is effective forretaining the threshold for a programming cell. The upper silicon oxidefilm 203 is effective for retaining the threshold for an erasing cell.

Providing the upper silicon oxide film 203 enables the prevention ofproblems such as possible oxygen vacancies in the high dielectricconstant insulating film 202 caused by a reducing atmosphere (forexample, a silane (SiH₄) gas atmosphere) in which the control gateelectrode film 21 is formed. A reduction in oxygen vacancies in the highdielectric constant insulating film 202 makes it possible to inhibit anincrease in leakage current and a decrease in breakdown voltage.Providing the silicon oxide films 201 and 203 on the respective sides ofthe high dielectric constant insulating film 202 allows the siliconoxide films 201 and 203 to supply oxygen to oxygen vacancies generatedin the step of forming a high dielectric constant insulating film 202and the subsequent steps. As a result, the oxygen vacancies can bereduced.

Further, by providing the silicon oxide films 201 and 203 with a largebarrier height on the respective sides of the high dielectric constantinsulating film 202, it is possible to reduce charge (trapped charge)trapped in the high dielectric constant insulating film during aprogramming/erasing operation. Furthermore, trapped charge is unlikelyto be emitted toward the control gate electrode 21 or floating gateelectrode 13. Such an excellent trap characteristic makes it possible toinhibit a variation in the threshold for each memory cell.

The silicon oxide films 201 and 203 desirably have a large filmthickness in connection with the supply of oxygen to the high dielectricconstant insulating film 202. When the silicon oxide films 201 and 203have a film thickness of at least 1.5 nm, the characteristics of thehigh dielectric constant insulating film 202 can be improved by oxygensupply. Accordingly, at least one of the silicon oxide films 201 and 203desirably has a film thickness of at least 1.5 nm. If the highdielectric constant insulating film 202 contains transition metal,oxygen vacancies are likely to occur. Thus, silicon oxide films ofthickness at least 2 nm are desirably provided in order to produce asufficient characteristic improving effect.

To effectively feed oxygen from the silicon oxide films 201 and 203 tothe high dielectric constant insulating film 202, the silicon oxidefilms 201 and 203 desirably have a film thickness greater than that ofthe high dielectric constant insulating film 202. Setting the filmthickness as described above enables oxygen to be sufficiently fed tothe entire high dielectric constant insulating film 202 in the filmthickness direction, allowing oxygen vacancies to be sufficientlyreduced.

FIG. 7 is a diagram showing the relationship between film thicknessratio (the film thickness of the silicon oxide film/the film thicknessof the high dielectric constant insulating film) and a leakage current(a leakage current generated during reading from a memory cell). Thelower silicon oxide film 201 and the upper silicon oxide film 203 havethe same film thickness. Although hafnium aluminium oxide (hafniumaluminate: HfAlO) is used for the high dielectric constant insulatingfilm 202, similar characteristics are obtained by using aluminium oxide(alumina: Al₂O₃). As is apparent from FIG. 7, setting the film thicknessof the silicon oxide films 201 and 203 greater than that of the highdielectric constant insulating film 202 enables the leakage current tobe sharply reduced. The film thickness of the silicon oxide filmssmaller than that of the high dielectric constant insulating filmresults in the formation of a leakage path attributed to oxygenvacancies in the high dielectric constant insulating film. This preventsa sufficient reduction in leakage current. The film thickness of thesilicon oxide films greater than that of the high dielectric constantinsulating film enables a sufficient reduction in oxygen vacancies inthe high dielectric constant insulating film. This makes it possible tosharply reduce the leakage current.

Thus, at least one of the lower silicon oxide film 201 and the uppersilicon oxide film 203 has a greater film thickness than the highdielectric constant insulating film 202.

As described above, the high dielectric constant insulating film 202 hasa greater relative dielectric constant than a typical silicon nitridefilm (Si₃N₄); the typical silicon nitride film has a relative dielectricconstant of about 7. Consequently, an inter-electrode insulating film isobtained which has a greater dielectric constant than a stack film (whatis called an ONO film) in which a silicon nitride film is providedbetween the silicon oxide films. Specifically, the high dielectricconstant insulating film 202 may be formed as described below.

For example, the high dielectric constant insulating film 202 may be analuminium oxide (Al₂O₃) film with a relative dielectric constant ofabout 8, a magnesium oxide (MgO) film with a relative dielectricconstant of about 10, a yttrium oxide (Y₂O₃) film with a relativedielectric constant of about 16, or a hafnium oxide (HfO₂) film,zirconium oxide (ZrO₂) film, or lanthanum oxide (La₂O₃) film with arelative dielectric constant of about 22. The high dielectric constantinsulating film 202 may also be a hafnium aluminate (HfAlO) film or thelike which is formed of an oxide consisting of two types of metals. Thehigh dielectric constant insulating film 202 may also be a hafniumsilicate (HfSiO) film or the like which is metal silicate. The highdielectric constant insulating film 202 may also contain nitrogen. Thatis, the high dielectric constant insulating film 202 may comprise anoxide or an oxinitirde containing a metal component such as aluminium(Al), magnesium (Mg), yttrium (Y), hafnium (Hf), zirconium (Zr), orlanthanum (La).

The present inventors have found that the above high dielectric constantmaterial reduces a leakage current of the inter-electrode insulatingfilm when a high electric field of at least about 10 MV/cm is appliedfor a programming/erasing operation, and increases memory operationspeed. This effect is particularly significantly exerted by materialshaving a greater work function than silicon nitrides or having a greatertrap density.

If the high dielectric constant insulating film 202 contains transitionmetal such as Y, Zr, Hf, or La, the catalytic action of the transitionmetal generates much active oxygen in an oxidation atmosphere during themanufacturing process (for example, an oxidizing step after theformation of the high dielectric constant insulating film 202, anoxidizing step after the formation of the upper silicon oxide film 203,an electrode sidewall oxidizing step after processing of the electrode,or the like). This makes it possible to improve the high dielectricconstant insulating film 202 and the silicon oxide films 201 and 203.Accordingly, the containment of the transition metal is suitable for thecase where the inter-electrode insulating film needs to offer excellentinsulating characteristics (reduced leakage current, improved breakdownvoltage, reduced trapped charge, and the like). In particular, the aboveimprovement is effective when the high dielectric constant insulatingfilm 202 is an oxide. This is expected to be due to the high efficiencywith which active oxygen is generated or diffused.

As described below, to achieve the effective improvement, the followingis preferably satisfied:

T/(T+M+S)≧0.2

where T is the concentration of the transition metal element in the highdielectric constant insulating film 202 (T>0), M is the concentration ofa metal element other than the transition metal element in the highdielectric constant insulating film 202 (M≧0), and S is theconcentration of a semiconductor element (for example, Si or Ge) in thehigh dielectric constant insulating film 202 (S≧0).

FIG. 8 is a diagram showing the relationship between the transitionmetal element concentration (T/(T+M+S)) and the thickness of aninterface layer. Samples used for measurements were obtained by forminghafnium aluminate (HfAlO) on a silicon substrate as a high dielectricconstant insulating film and then performing a heat treatment in anoxygen atmosphere at 700° C. for 30 minutes. An Hf concentration(transition metal element concentration) of at least 20% increases thethickness of the interface layer formed between the silicon substrateand the hafnium aluminate film. This is because the catalytic action ofHf allows much active oxygen to be fed to the surface of the siliconsubstrate. A similar catalytic effect can also be produced by transitionmetals (Y, Zr, La, and the like) other than Hf. Accordingly, thetransition metal element concentration (T/(T+M+S)) is desirably at least20%.

On the other hand, if the high dielectric constant insulating film 202comprises aluminium oxide or magnesium oxide containing no transitionmetal, the above catalytic action is suppressed. This makes it possibleto reduce the amount of oxidation of a bird's beak formed at theinterface between the silicon oxide films 201 and 203 and the controlgate electrode 21 and floating gate electrode 13. This in turn inhibitsa decrease or variation in the electric capacitance of theinter-electrode insulating film 20. Therefore, if the capacitance ratio(coupling ratio) of the inter-electrode insulating film 20 to the tunnelinsulating film 12 needs to be controllable, a high dielectric constantinsulating film containing no transition metal is desirable.

The crystal state of the high dielectric constant insulating film 202may be any of an amorphous state, an amorphous state containing amicrocrystal, a polycrystal, and a single crystal. However, the leakagecurrent of the high dielectric constant insulating film and the filmdensity have a correlation; a higher density more significantly reducesthe leakage current. The polycrystal and single crystal offers a highcrystallinity and enables an increase in film density. Thus, the highdielectric constant insulating film 202 is desirably a polycrystallinefilm or a single crystal film. Further, if the high dielectric constantinsulating film 202 is polycrystalline, the high dielectric constantinsulating film 202 and the silicon oxide films 201 and 203 can besufficiently improved. This is expected to be due to the sufficientsupply of an oxidizer to the silicon oxide film through the crystalgrain boundary of the high dielectric constant insulating film.Therefore, the high dielectric constant insulating film 202 is desirablyformed of a polycrystalline film.

To improve the silicon oxide film by supplying an oxidizer through thecrystal grain boundary, it is desirable to set the size (average grainsize, average grain diameter) of crystal grains equal to or smaller than100 nm. This value is expected to depend on the diffusion length of theoxidizer. For a sufficient improvement effect, it is desirable thatcrystal grain size is smaller than that of the memory cell. For example,a columnar crystal having a crystal grain size of at most 10 nm.

In view of the leakage characteristic of the high dielectric constantinsulating film, the crystal grains contained in the high dielectricconstant insulating film desirably have an average grain size (averagegrain diameter) of at least 5 nm. This is because an average grain sizeof less than 5 nm reduces the film density, preventing a reduction inleakage current. FIG. 9 is a diagram showing the relationship betweenthe average grain size and the leakage current. Although hafniumaluminate (HfAlO) is used for the high dielectric constant insulatingfilm, similar characteristics are obtained by using aluminium oxide(Al₂O₃). FIG. 9 shows that an average grain size of less than 5 nmincreases the amount of leakage current.

Thus, the crystal grains contained in the high dielectric constantinsulating film 202 desirably have an average grain size (average graindiameter) of at least 5 nm. Further, the crystal grains contained in thehigh dielectric constant insulating film 202 desirably have an averagegrain size (average grain diameter) of at most 100 nm.

The crystal grain boundary of the crystal grains contained in the highdielectric constant insulating film 202 desirably penetrates the highdielectric constant insulating film 202 in its thickness direction. Thisallows the silicon oxide films 201 and 203 to be more effectivelyimproved. The crystal grain boundary penetrating the high dielectricconstant insulating film 202 enables an oxidizer be sufficientlysupplied to the silicon oxide films 201 and 203 in an oxidationatmosphere step after the formation of an inter-electrode insulatingfilm or the processing of electrodes. The silicon oxide films 201 and203 are thus effectively improved.

The thickness of the high dielectric constant insulating film 202 equalto or greater than that of one atomic layer reduces the leakage currentof the inter-electrode insulating film during a programming/erasingoperation and increases the memory operation speed. A thicker highdielectric constant insulating film more significantly exerts thiseffect. However, an excessively thick high dielectric constantinsulating film degrades the data retention characteristic of the memorycell. This is because the excessively thick high dielectric constantinsulating film increases the amount of leakage current at a lowelectric field and increases the amount of charge trapped. The increasein the amount of low electric field leakage current is expected to bedue to the small barrier height of the high dielectric constantinsulating film. Electric conduction resulting from the trap level ofthe high dielectric constant insulating film is also expected to be afactor that causes low electric field leakage. Setting the filmthickness of the high dielectric constant insulating film equal to orsmaller than 5 nm makes it possible to inhibit the data retentioncharacteristic from being degraded.

FIG. 10 is a diagram showing the relationship between the number ofcycles for the growth of atomic layers of the high dielectric constantinsulating film 202 and the leakage current. Although aluminium oxide(Al₂O₃) is used for the high dielectric constant insulating film,similar characteristics are obtained by using hafnium aluminate (HfAlO).FIG. 10 shows that the leakage current is reduced by the execution of atleast one cycle, that is, the formation of at least one atomic layer ofthe high dielectric constant insulating film.

FIG. 11 is a diagram showing the relationship between the film thicknessof the high dielectric constant insulating film 202 and the low electricfield leakage current. Although aluminium oxide (Al₂O₃) is used for thehigh dielectric constant insulating film, similar characteristics areobtained by using hafnium aluminate (HfAlO). FIG. 11 shows that theleakage current increases rapidly when the film thickness of the highdielectric constant insulating film exceeds 5 nm.

Thus, the thickness of the high dielectric constant insulating film 202is desirably equal to or greater than that of one atomic layer and equalto or smaller than 5 nm.

If the high dielectric constant insulating film 202 is formed of aninsulating film containing transition metal, a large amount of charge istrapped. Accordingly, to provide the memory cell with a sufficient dataretention characteristic, it is desirable to set the film thickness ofthe high dielectric constant insulating film 202 equal to or smallerthan 4 nm.

FIGS. 12A and 12B are sectional views showing in detail a part of theprocess for manufacturing a semiconductor device shown in FIGS. 1A and1B to 5A and 5B and 6A and 6B. FIG. 12A is a sectional view in the bitline direction (channel length direction). FIG. 12B is a sectional viewin the word line direction (channel width direction).

After the steps shown in FIGS. 3A and 3B, a lower silicon oxide film 201of thickness about 1 to 5 nm is formed by CVD on the exposed surfaces ofthe polycrystalline silicon film (floating gate electrode film) 13 andthe silicon oxide film (isolation insulating film) 17. An aluminiumoxide film as a high dielectric constant insulating film 202 issubsequently formed on the surface of the lower silicon oxide film 201by ALD (Atomic Layer Deposition). The film thickness of the aluminumoxide film 202 is equal to or greater than that of one atomic layer andequal to or smaller than 5 nm. Further, an upper silicon oxide film 203of thickness about 1 to 5 nm is formed on the surface of the aluminiumoxide film 202 by CVD. This results in an inter-electrode insulatingfilm 20 formed of the lower silicon oxide film 201, high dielectricconstant insulating film 202, and upper silicon oxide film 203. Thesubsequent steps are similar to those shown in FIGS. 1A and 1B to 5A and5B.

With the above manufacturing method, the lower silicon oxide film 201and upper silicon oxide film 203 are formed by CVD. However, a methodsuch as ALD, thermal oxidation, radical oxidation, or sputtering may beused.

Further, with the above manufacturing method, the high dielectricconstant insulating film 202 is formed by ALD. However, a method such asCVD or sputtering may be used. The present manufacturing methoddesirably uses ALD in order to ensure a uniform film thickness and toinhibit a variation in characteristics among the memory cells.

With the above manufacturing method, the high dielectric constantinsulating film 202 formed may be heat-treated at a temperature higherthan its formation temperature. The high temperature heat treatmentmakes it possible to improve the film quality of the high dielectricconstant insulating film 202 and increases its density, providing a highdielectric constant insulating film 202 with excellent characteristics.

If the high dielectric constant insulating film 202 is formed of metaloxide such as aluminium oxide, it is formed by CVD or ALD using steam(water vapor), which diffuses readily in the insulating film, as oxygensource gas to supply steam to the entire lower silicon oxide film 201.This improves the insulating property of the lower silicon oxide film201. In this case, a sufficient amount of steam can also be supplied tothe interface between the lower silicon oxide film 201 and thepolycrystalline silicon film (floating gate electrode film) 13. Thisimproves an interface trap characteristic. Thus, steam (water vapor) canbe effectively used as oxygen source gas to prevent the possible leakageof charge from the floating gate electrode 13 to the control gateelectrode 21.

If the high dielectric constant insulating film 202 is formed of metaloxide such as aluminium oxide, it is formed by CVD or ALD using ozone oroxygen radicals, which have a small diffusion length in insulating filmbut a high oxidation power, as oxygen source gas. This significantlyimproves the insulating property of the surface area of the lowersilicon oxide film 201. Therefore, ozone or oxygen radicals can beeffectively used as oxygen source gas in order to recover the filmquality of the lower silicon oxide film 201, for example, if reducinggas or halogen-containing gas, which may significantly degrade the filmquality of the surface area of the lower silicon oxide film 201, is usedas source gas for the high dielectric constant insulating film 202.

Description will be given below of the case where the high dielectricconstant insulating film 202 is formed by CVD or ALD using ozone asoxygen source gas (oxidizer). Specifically, an aluminium oxide film isformed by ALD using ozone (O₃) as an oxygen source and trimethylaluminium (Al(CH₃)₃) as an aluminium source.

The aluminium source is introduced into a reaction furnace to form analuminium layer. Then, the reaction furnace is subjected to evacuationand purging with inert gas. Ozone is subsequently introduced into thereaction furnace to oxidize the aluminium layer, forming aluminiumoxide. After evacuation and purging with inert gas, an aluminium sourceis introduced into the reaction furnace again. Thus, the alternateintroduction of the aluminium source and ozone (oxygen source) into thereaction furnace results in the formation of an aluminium oxide film.Film formation pressure is at most 50 Torr, and film formationtemperature is about 300° C.

FIG. 28 is a diagram showing the amount of fixed charge in the memorycell when ozone (O₃) or steam (H₂O) is used as an oxygen source for thealuminium oxide film. As is apparent from FIG. 28, the use of ozone asan oxygen source enables a reduction in the fixed charge in memory cell.This is expected to be because the use of ozone as an oxygen sourceenables a reduction in carbon emitted from the aluminium oxide filmduring a subsequent thermal step. Carbon is expected to migrate from thealuminium oxide film on the isolation insulating film (silicon oxidefilm) to an element area via the isolation insulating film, where itbecomes fixed charge. The fixed charge may vary the threshold of thememory cell. Therefore, the use of ozone as an oxygen source enablesdevice characteristics to be improved.

The film formation temperature for the aluminium oxide film ispreferably between 150° C. and 300° C. as shown below.

The resistance of the aluminium oxide film to chemicals depends on thefilm formation temperature. Forming an aluminium oxide film at atemperature higher than 300° C. reduces the resistance of the aluminiumoxide film to chemicals. FIG. 29 is a diagram showing the relationshipbetween the film formation temperature of the aluminium oxide film andthe etching amount observed when diluted fluorinated acid is used as achemical. FIG. 29 shows that the etching amount increases at a filmformation temperature of higher than 300° C. Therefore, the filmformation temperature of the aluminium oxide film is preferably at most300° C.

Setting the film formation temperature of the aluminium oxide film lowerthan 150° C. increases the concentration of carbon in the aluminiumoxide film. For example, this reduces the film density and increases theamount of leakage current and fixed charge in the memory cell. FIG. 30is a diagram showing the relationship between the film formationtemperature of the aluminium oxide film and a flat band voltage shift(Vfb shift) in the memory cell. FIG. 30 shows that a film formationtemperature of lower than 150° C. increases the magnitude of the Vfbshift, that is, increases the amount of fixed charge. Accordingly, thefilm formation temperature of the aluminium oxide film is preferably atleast 150° C. FIG. 30 also shows the results obtained when a hafniumaluminium oxide (HfAlO) is used as a high dielectric constant insulatingfilm. When the hafnium aluminium oxide film is used, its film formationtemperature is preferably at least 175° C.

When an aluminium oxide film or a hafnium aluminium oxide film isformed, effects similar to those described above can be exerted by usingoxygen radical instead of ozone as an oxygen source.

As described above, to improve the film quality of the high dielectricconstant insulating film 202 and increase its density, the highdielectric constant insulating film 202 formed is preferablyheat-treated at a temperature higher than its formation temperature.This makes it possible to, for example, reduce the leakage current,improve the resistance to chemicals, and inhibit possible defects(oxygen vacancies and metal vacancies) in the aluminium oxide filmduring the thermal step. The heat treatment may be performed in an inertgas atmosphere or in an oxidizing gas atmosphere. To inhibit possibleoxygen vacancies during the thermal step, the oxidizing atmosphere ispreferably used. To inhibit a possible increase in film thicknessresulting from the heat treatment, the inert gas atmosphere ispreferably used.

The temperature of the heat treatment after the formation of analuminium oxide film is preferably at least 1,000° C. A heat treatmenttemperature of at least 1,000° C. enables etching resistance to besignificantly improved. This makes it possible to inhibit a possiblevariation in the amount of side etching of the high dielectric constantinsulating film and a possible variation in the coupling ratio(C2/(C1+C2)) of the memory cell. Further, the large side etching amountof the high dielectric constant insulating film increases the amount ofhigh electric field leakage, degrading the programming/erasingcharacteristic of the memory cell. The above high temperature thermalprocess enables the etching resistance to be significantly improved,allowing the prevention of the above problems.

FIG. 31 is a diagram showing the relationship between the heat treatmenttemperature used after the formation of an aluminium oxide film and theetching amount (etching rate) of the aluminium oxide film with dilutedfluorinated acid. FIG. 31 shows that a heat treatment temperature of atleast 1,000° C. sharply reduces the etching amount (etching rate) of thealuminium oxide film. Consequently, the heat treatment temperature usedafter the formation of the aluminium oxide film is preferably at least1,000° C. The time for the heat treatment is preferably at least onesecond. FIG. 31 also shows the results obtained when a hafnium aluminiumoxide (HfAlO) film is used as a high dielectric constant insulatingfilm. As shown in FIG. 31, when the hafnium aluminium oxide film isused, the heat treatment temperature used after its formation ispreferably at least 900° C.

The aluminium source used to form a high dielectric constant insulatingfilm such as an aluminium oxide film or a hafnium aluminium oxide filmis not limited to trimethyl aluminium (Al(CH₃)₃). For example, thealuminium source may be obtained by changing the methyl group oftrimethyl aluminium to an alkyl group (ethyl group or propyl group)having a larger carbon number than the methyl group. Alternatively, thealuminium source may be obtained by changing the methyl group oftrimethyl aluminium to an alkoxide group such as a methoxy group.

The use of trimethyl aluminium as an aluminium source enables theformation of a high dielectric constant insulating film with a reducedcarbon content. This also enables the formation of a high dielectricconstant insulating film with improved uniformity and step coverage.Further, the use of an aluminium source having an alkyl group with alarger carbon number than the methyl group or having an alkoxide groupincreases the decomposition temperature of the source and thus the filmformation temperature. The increased film formation temperature enablesan increase in film density. The increased film formation temperaturemakes it possible to promote the improvement of the lower insulatingfilm or the interface between the lower insulating film and the highdielectric constant insulating film based on the oxygen source(oxidizer).

Embodiment 2

Now, a second embodiment of the present invention will be described. Abasic configuration and a basic manufacturing method in accordance withthe second embodiment are similar to those in FIGS. 1A and 1B to 5A and5B for the first embodiment and will not be described in detail. Thematters described in the first embodiment will not be described indetail.

FIG. 13 is a sectional view of a nonvolatile semiconductor memory devicein accordance with the present embodiment in the bit line direction(channel length direction). Components corresponding to those shown inFIGS. 1A and 1B to 5A and 5B are denoted by the same reference numeralsand will not be described in detail.

As shown in FIG. 13, the inter-electrode insulating film 20 is formed ofa stack film including a lower silicon nitride film 204, a highdielectric constant insulting film (intermediate insulating film) 202formed on the lower silicon nitride film 204, and an upper siliconnitride film 205 formed on the high dielectric constant insulating film202. The high dielectric constant insulating film 202 contains at leasta metal element and has a relative dielectric constant greater than 7.That is, the high dielectric constant insulating film 202 has a relativedielectric constant greater than that (about 7) of a typical siliconnitride film (Si₃N₄). The high dielectric constant insulating film 202preferably contains oxygen in addition to a metal element.

As described above, the inter-electrode insulating film 20 has the stackstructure including the lower silicon nitride film 204, high dielectricconstant insulating film 202, and upper silicon nitride film 205. Theinsulating property of the high dielectric constant insulating film 202is thus significantly improved. This makes it possible to ensure amemory retention characteristic, avoid memory malfunctions, and providea sufficient memory operation speed. It is possible to inhibit avariation in the coupling ratio of the memory cell, sharply reducing avariation in memory cell characteristics.

The high dielectric constant insulating film is likely to undergo filmstructure defects such as oxygen vacancies as a result of the adverseeffect of a reducing agent such as hydrogen (for example, hydrogencontained in a polycrystalline silicon film used as a floating gateelectrode or control gate electrode) emitted from surrounding filmsduring the manufacturing process. In the present embodiment, the siliconnitride films 204 and 205 are provided which can sufficiently inhibitthe possible diffusion of the reducing agent such as hydrogen. Thismakes it possible to prevent the reducing agent from diffusing to thehigh dielectric constant insulating film 202 even though films areexposed to the reducing atmosphere during the manufacturing process.Thus, possible oxygen vacancies can be significantly inhibited,drastically improving the insulating property of the high dielectricconstant insulating film.

The silicon nitride films 204 and 205, which can effectively inhibit thepossible diffusion of the oxidizer, enables the prevention of oxidationof a bird's beak formed at the interface between the inter-electrodeinsulating film 20 and the control gate electrode 21 and at theinterface between the inter-electrode insulating film 20 and thefloating gate electrode 13.

Owing to its barrier height greater than that of the high dielectricconstant insulating film, the silicon nitride film is effective inreducing a low electric field leakage current. The provision of thelower silicon nitride film 204 makes it possible to effectively preventthe metal element or the like contained in the high dielectric constantinsulating film 202 from diffusing to the tunnel insulating film 12 orthe isolation insulating film 17. This makes it possible to avoid thedegradation of the insulating property of the tunnel insulating film 12or the isolation insulating film 17.

Setting the thickness of the silicon nitride films 204 and 205 equal toor greater than 0.5 mm enables the inhibition of possible oxygenvacancies due to the reducing agent and the possible formation of abird's beak at the electrode interface. If the high dielectric constantinsulating film 202 contains transition metal, the reducing agent causesmany oxygen vacancies. To ensure a sufficient insulating property, thesilicon nitride films 204 and 205 desirably have a film thickness of atleast 0.8 nm.

If the high dielectric constant insulating film 202 contains transitionmetal such as Y, Zr, Hf, or La, the catalytic action of the transitionmetal generates much active oxygen in an oxidation atmosphere during themanufacturing process (for example, an oxidizing step after theformation of the high dielectric constant insulating film 202, anelectrode sidewall oxidizing step after processing of the electrode, orthe like). This makes it possible to improve the high dielectricconstant insulating film 202. Accordingly, the containment of thetransition metal is suitable for the case where the inter-electrodeinsulating film needs to offer excellent insulating characteristics(reduced leakage current, improved breakdown voltage, reduced trappedcharge, and the like). In particular, the above improvement is effectivewhen the high dielectric constant insulating film 202 is an oxide. Thisis expected to be due to the high efficiency with which active oxygen isgenerated or diffused. As described in the first embodiment, to achievethe effective improvement, the following is preferably satisfied:

T/(T+M+S)≧0.2

where T is the concentration of the transition metal element in the highdielectric constant insulating film 202 (T>0), M is the concentration ofa metal element other than the transition metal element in the highdielectric constant insulating film 202 (M≧0), and S is theconcentration of a semiconductor element (for example, Si or Ge) in thehigh dielectric constant insulating film 202 (S≧0).

On the other hand, if the high dielectric constant insulating film 202comprises aluminium oxide or magnesium oxide containing no transitionmetal, the above catalytic action is suppressed. This makes it possibleto prevent the silicon nitride films 204 and 205 from being partlyoxidized into silicon oxide films during an electrode sidewall oxidizingstep after electrode processing. This in turn inhibits a decrease orvariation in the electric capacitance of the inter-electrode insulatingfilm 20. Therefore, if the electric capacitance ratio (coupling ratio)of the inter-electrode insulating film 20 to the tunnel insulating film12 needs to be controllable, a high dielectric constant insulating filmcontaining no transition metal is desirable.

FIGS. 14A and 14B are sectional views showing in detail a part of theprocess for manufacturing a semiconductor device shown in FIGS. 1A and1B to 5A and 5B and 13. FIG. 14A is a sectional view in the bit linedirection (channel length direction). FIG. 14B is a sectional view inthe word line direction (channel width direction).

After the steps shown in FIGS. 3A and 3B, a lower silicon nitride film204 of thickness about 0.5 to 10 nm is formed by CVD on the exposedsurfaces of the polycrystalline silicon film (floating gate electrodefilm) 13 and the silicon oxide film (isolation insulating film) 17. Ahafnium oxide film as a high dielectric constant insulating film 202 issubsequently formed on the surface of the lower silicon nitride film 204by ALD (Atomic Layer Deposition). The film thickness of the hafniumoxide film 202 is equal to or greater than that of one atomic layer andequal to or smaller than 5 nm. Further, an upper silicon nitride film205 of thickness about 0.5 to 10 nm is formed on the surface of thehafnium oxide film 202 by CVD. This results in an inter-electrodeinsulating film 20 formed of the lower silicon nitride film 204, highdielectric constant insulating film 202, and upper silicon nitride film205. The subsequent steps are similar to those shown in FIGS. 1A and 1Bto 5A and 5B.

With the above manufacturing method, the lower silicon nitride film 204and upper silicon nitride film 205 are formed by CVD. However, a methodsuch as ALD, thermal nitriding, radical nitriding, or sputtering may beused.

Further, with the above manufacturing method, the high dielectricconstant insulating film 202 is formed by ALD. However, a method such asCVD or sputtering may be used. The present manufacturing methoddesirably uses ALD in order to ensure a uniform film thickness and toinhibit a variation in characteristics among the memory cells.

With the above manufacturing method, the high dielectric constantinsulating film 202 formed may be heat-treated at a temperature higherthan its formation temperature as described in the first embodiment. Thehigh temperature heat treatment makes it possible to improve the filmquality of the high dielectric constant insulating film 202 andincreases its density, providing a high dielectric constant insulatingfilm 202 with excellent characteristics.

Although described below in a third embodiment in detail, the lowersilicon nitride film 204 formed may be heat-treated at a temperaturehigher than its formation temperature. The high temperature heattreatment makes it possible to improve the film quality of the lowersilicon nitride film 204.

If the high dielectric constant insulating film 202 is formed of metaloxide such as hafnium oxide, it is formed by CVD or ALD using steam(water vapor), which is unlikely to oxidize the silicon nitride film, asoxygen source gas, enabling the inhibition of a decrease in the filmthickness of the lower silicon nitride film 204. Thus, steam can beeffectively used as oxygen source gas to prevent a possible variation inthe electric capacitance of the inter-electrode insulating film 20.

If the high dielectric constant insulating film 202 is formed of metaloxide such as hafnium oxide, it is formed by CVD or ALD using ozone oroxygen radicals, which have high oxidation power, as oxygen source gas.This enables the sufficient oxidation of the interface between the lowersilicon nitride film 204 and the high dielectric constant insulatingfilm 202. The interface trap characteristic is thus drasticallyimproved. Therefore, ozone or oxygen radicals can be effectively used asoxygen source gas in order to prevent a possible variation in thethreshold for the memory cell caused by the trapping of charge in theinter-electrode insulating film 20.

Embodiment 3

Now, a third embodiment of the present invention will be described. Abasic configuration and a basic manufacturing method in accordance withthe third embodiment are similar to those in FIGS. 1A and 1B to 5A and5B for the first embodiment and will not be described in detail. Thematters described in the first embodiment will not be described indetail.

FIG. 15 is a sectional view of a nonvolatile semiconductor memory devicein accordance with the present embodiment in the bit line direction(channel length direction). Components corresponding to those shown inFIGS. 1A and 1B to 5A and 5B are denoted by the same reference numeralsand will not be described in detail.

As shown in FIG. 15, the inter-electrode insulating film 20 is formed ofa stack film including the lower silicon nitride film 204, the lowersilicon oxide film 201 formed on the lower silicon nitride film 204, thehigh dielectric constant insulting film (intermediate insulating film)202 formed on the lower silicon oxide film 201, the upper silicon oxidefilm 203 formed on the high dielectric constant insulating film 202, andthe upper silicon nitride film 205 formed on the upper silicon oxidefilm 203. The high dielectric constant insulating film 202 contains atleast a metal element and has a relative dielectric constant greaterthan 7. That is, the high dielectric constant insulating film 202 has arelative dielectric constant greater than that (about 7) of a typicalsilicon nitride film (Si₃N₄). The high dielectric constant insulatingfilm 202 preferably contains oxygen in addition to a metal element.

As described above, the inter-electrode insulating film 20 has the stackstructure including the lower silicon nitride film 204, lower siliconoxide film 201, high dielectric constant insulating film 202, uppersilicon oxide film 203, and upper silicon nitride film 205. Thisstructure enables the simultaneous exertion of the effects described inthe first and second embodiments (the supply of the oxidizer to the highdielectric constant insulating film 202, the inhibition of diffusion ofthe reducing agent to the high dielectric constant insulating film 202,the inhibition of formation of a bird's beak, and the like).

The lower silicon nitride film 204 provided under the lower siliconoxide film 201 enables the prevention of possible disadvantageousformation of a new silicon oxide layer on the surface of the floatinggate electrode 13 as a result of the step of forming silicon oxide films201 and 203 and a high dielectric constant insulating film 202 or theoxidation atmosphere step for improving the silicon oxide films 201 and203 and high dielectric constant insulating film 202. This allows theprevention of a possible increase or variation in the electriccapacitance of the inter-electrode insulating film 20. Further, a moresufficient oxidizing process can be executed in the step of formingsilicon oxide films 201 and 203 and a high dielectric constantinsulating film 202 or the oxidation atmosphere step for improving thesilicon oxide films 201 and 203 and high dielectric constant insulatingfilm 202. The insulating property of the inter-electrode insulating film20 can thus be improved.

Furthermore, the upper silicon nitride film 205 provided over the uppersilicon oxide film 203 enables the prevention of possible detachment ofoxygen from the high dielectric constant insulating film 202 through theupper silicon oxide film 203. This also enables the prevention ofpossible, disadvantageous formation of a new silicon oxide layer at theinterface of the control electrode 21 as a result of the detachment ofoxygen from the upper silicon oxide film 203 or high dielectric constantinsulating film 202. This in turn allows the prevention of a possible,disadvantageous increase in the electric capacitance of theinter-electrode insulating film.

Further, since all the three layers, that is, the lower silicon oxidefilm 201, high dielectric constant insulating film 202, and uppersilicon oxide film 203, are formed of an oxide, the oxidizer can beallowed to simultaneously permeate all the three layers. That is, toimprove the characteristics of the inter-electrode insulating film, itis important to compensate for oxygen vacancies occurring during filmformation. A treatment for oxygen supply after the formation of thethree layers enables all the three layers to be simultaneously improved.In contrast, if the inter-electrode insulating film is formed of threelayers, a silicon oxide film, a silicon nitride film, and a siliconoxide film, the silicon nitride film functions as an oxygen diffusionbarrier. Thus, to improve the quality of the lower and upper siliconoxide films, an oxidizing process for improvement needs to be executedafter the formation of a lower silicon oxide film and the formation ofan upper silicon oxide film. Further, since a silicon nitride film isformed after the oxidation and improvement of the lower silicon oxidefilm, damage disadvantageously cannot be completely be eliminated fromthe lower silicon oxide film after the formation of a silicon nitridefilm. The present embodiment can reliably prevent such a problem.

FIGS. 16A and 16B are sectional views showing in detail a part of theprocess for manufacturing a semiconductor device shown in FIGS. 1A and1B to 5A and 5B and 15. FIG. 16A is a sectional view in the bit linedirection (channel length direction). FIG. 16B is a sectional view inthe word line direction (channel width direction).

After the steps shown in FIGS. 3A and 3B, a lower silicon nitride film204 of thickness about 0.5 to 10 nm is formed by radical nitriding onthe exposed surfaces of the polycrystalline silicon film (floating gateelectrode film) 13 and the silicon oxide film (isolation insulatingfilm) 17. A lower silicon oxide film 201 of thickness 1 to 5 nm issubsequently formed by CVD on the surface of the lower silicon nitridefilm 204. A hafnium aluminate (HfAlO) film as a high dielectric constantinsulating film 202 is subsequently formed on the surface of the lowersilicon oxide film 201 by ALD (Atomic Layer Deposition). The filmthickness of the hafnium aluminate film 202 is equal to or greater thanthat of one atomic layer and equal to or smaller than 5 nm. An uppersilicon oxide film 203 of thickness 1 to 5 nm is subsequently formed onthe surface of the hafnium aluminate film 202 by CVD. Further, an uppersilicon nitride film 205 of thickness about 0.5 to 10 nm is formed onthe upper silicon oxide film 203 by CVD. This results in aninter-electrode insulating film 20 formed of the lower silicon nitridefilm 204, lower silicon oxide film 201, high dielectric constantinsulating film 202, upper silicon oxide film 203, and upper siliconnitride film 205. The subsequent steps are similar to those shown inFIGS. 1A and 1B to 5A and 5B.

With the above manufacturing method, the lower silicon nitride film 204,lower silicon oxide film 201, high dielectric constant insulating film202, upper silicon oxide film 203, and upper silicon nitride film 205can be formed by any of various methods including CVD, ALD, thermalnitriding, radical nitriding, and sputtering.

Further, with the above manufacturing method, the high dielectricconstant insulating film 202 is formed by ALD. However, a method such asCVD or sputtering may be used. The present manufacturing methoddesirably uses ALD in order to ensure a uniform film thickness and toinhibit a variation in characteristics among the memory cells.

With the above manufacturing method, the high dielectric constantinsulating film 202 formed may be heat-treated at a temperature higherthan its formation temperature as described in the first embodiment. Thehigh temperature heat treatment makes it possible to improve the filmquality of the high dielectric constant insulating film 202 andincreases its density, providing a high dielectric constant insulatingfilm 202 with excellent characteristics.

Further, the lower silicon nitride film 204 formed may be heat-treatedat a temperature higher than its formation temperature. The hightemperature heat treatment makes it possible to improve the film qualityof the lower silicon nitride film 204.

The desirable film formation temperature of the lower silicon oxide film201 is at most 600° C. This makes it possible to sharply reduce nitrogendetached from the lower silicon nitride film 204. This in turn enablesthe prevention of a possible decrease in the dielectric constant of thelower silicon nitride film 204. It is also possible to prevent thepossible oxidation of a bird's beak at the interface between thefloating gate electrode 13 and the lower silicon nitride film 204 causedby active oxygen generated by the catalytic effect of the metal elementin the high dielectric constant insulating film 202.

Further, the desired film formation temperature of the upper siliconoxide film 203 is at most 600° C. This makes it possible to sharplyreduce oxygen detached from the high dielectric constant insulating film202. This in turn enables the inhibition of possible formation of acharge trap level or a leakage current path in the high dielectricconstant insulating film 202. It is therefore possible to further reducethe leakage current of the inter-electrode insulating film 20 and avariation in the threshold for the memory cell caused by chargetrapping.

Methods for forming silicon oxide films 201 and 203 at most 600° C.include, for example, ALD using TDMAS (tridimethylaminosilane)(SiH[N(CH₃)₂]₃)) and ozone gas or oxygen radicals as source gas and ALDusing BTBAS (bi-tertialy butylamino silane) (SiH₂N[C(CH₃)₃]₂)) and ozonegas or oxygen radicals as source gas. Alternatively, the silicon oxidefilms 201 and 203 can be formed by sputtering in an atmospherecontaining oxygen, using silicon or silicon oxide as a target material.Effects similar to those described above can also be exerted by usingany other method provided that the silicon oxide films 201 and 203 areformed at most 600° C.

Description will be given below of a step of forming a lower siliconnitride film 204 by radical nitriding and a step of forming a lowersilicon nitride film 204 and then performing a heat treatment at atemperature higher than the formation temperature of the lower siliconnitride film 204.

For example, conditions for the radical nitriding include a highfrequency power of at least 500 W, a pressure of between several tens ofmTorr and 10 Torr, a nitriding treatment temperature of between the roomtemperature and 800° C., and a nitriding treatment time of between 5 and600 seconds.

A lower silicon nitride film 204 is formed by radical nitriding and thenheat-treated at a temperature higher than its formation temperature. Theheat treatment enables an increase in the density of the lower siliconnitride film 204. Further, an incomplete Si—N bond can be converted intoa complete Si—N bond. Therefore, the heat treatment enables theimprovement of film quality of the lower silicon nitride film 204 and ofthe device characteristics.

FIG. 32 is a diagram showing the effects of the heat treatment. Thermaltreatment temperature is 1,000° C., and heat treatment time is 30seconds. As shown in FIG. 32, the heat treatment after the formation ofa lower silicon nitride film corrects a variation in threshold. This isbecause the heat treatment improves the film quality of the lowersilicon nitride film and reduces the leakage current during chargeretention as well as the level of trapping.

Thus, the heat treatment enables an increase in the density of the lowersilicon nitride film 204. This allows the inhibition of possibleemission of nitrogen from the lower silicon nitride film 204, reducingthe fixed charge in the memory cell.

In order to inhibit a possible increase in the electrical film thicknessof the lower silicon nitride film 204, the above heat treatment ispreferably performed in an inert gas atmosphere. In order to improve thecharacteristics of the interface between the lower silicon nitride film204 and the upper insulating film, the above heat treatment ispreferably performed in an oxidizing atmosphere.

The heat treatment may be performed at a temperature higher than theformation temperature of the lower silicon nitride film 204. However, toexert sufficient effects, the heat treatment is preferably performed atleast 900° C. FIG. 33 is a diagram showing the relationship between theheat treatment temperature and a low electric field leakage current. Asshown in FIG. 33, a heat treatment at least 900° C. enables a reductionin low electric field leakage current.

In the above example, the lower silicon nitride film 204 is formed byradical nitriding. However, the lower silicon nitride film 204 may beformed by low pressure CVD or ALD.

Description will be given of the formation of a high dielectric constantinsulating film 202 by CVD or ALD using ozone as oxygen source gas(oxidizer). Specifically, a hafnium aluminium oxide (hafnium aluminate:HfAlO) film is formed by ALD using ozone (O₃) as a oxygen source anddiethyl aminohafnium (Hf(NC₂H₅)₄) as a hafnium source. To form a hafniumaluminium oxide film, the pressure is set at most 50 Torr and thetemperature is set at about 275° C.

The use of ozone (O₃) as an oxygen source for the hafnium aluminiumoxide film enables a reduction in the fixed charge in the memory cell asshown in FIG. 28 for the first embodiment. This is expected to bebecause the use of ozone as an oxygen source enables a reduction incarbon emitted from the hafnium aluminium oxide film during a subsequentthermal step. Reduction of the amount of oxidizer emitted from thehafnium aluminium oxide film is expected to be a factor of reducingfixed charges. The oxidizer emitted from the hafnium aluminium oxidefilm increases the amount of nitrogen emitted from the lower siliconnitride film and thus the amount of fixed charge in the memory cell. Thefixed charge may vary the threshold for the memory cell. Therefore, theuse of ozone as an oxygen source makes it possible to improve the devicecharacteristics.

The hafnium source used to form a hafnium aluminium oxide film is notlimited to diethyl aminohafnium (Hf(NC₂H₅)₄). For example, the hafniumsource may be obtained by changing the ethyl group of diethylaminohafnium to other alkyl group. Alternatively, the hafnium source maybe obtained by changing the ethyl group of diethyl aminohafnium to analkoxide group.

The film formation temperature of the hafnium aluminium oxide film ispreferably at most 300° C. Setting the film formation temperature of thehafnium aluminium oxide film higher than 300° C. may significantlydegrade the surface morphology of the hafnium aluminium oxide film.Setting the film formation temperature of the hafnium aluminium oxidefilm higher than 300° C. forms grains at the surface of the hafniumaluminium oxide film. The density of grains increases consistently withthe film formation temperature. On the other hand, no grains wereobtained at the surface of the hafnium aluminium oxide film when thefilm formation temperature of the hafnium aluminium oxide film is set at290° C. Therefore, the film formation temperature of the hafniumaluminium oxide film is preferably at most 300° C.

Further, the film formation temperature of the hafnium aluminium oxidefilm is preferably at least 175° C. As already shown in FIG. 30, settingthe film formation temperature of the hafnium aluminium oxide film lowerthan 175° C. increases the magnitude of the Vfb shift, that is, theamount of fixed charge. Therefore, the film formation temperature of thehafnium aluminium oxide film is preferably at least 175° C.

In the formation of a hafnium aluminium oxide film, effects similar tothose described above can be exerted by using oxygen radicals as anoxygen source in place of ozone.

As already described, to improve the film quality of the high dielectricconstant insulating film (hafnium aluminium oxide film) 202 andincreases its density, the high dielectric constant insulating film 202formed is preferably heat-treated at a temperature higher than itsformation temperature. This makes it possible to, for example, reducethe leakage current, improve the resistance to chemicals, and inhibitpossible defects (oxygen vacancies and metal vacancies) in the hafniumaluminium oxide film during the thermal step. The heat treatment may beperformed in an inert gas atmosphere or in an oxidizing gas atmosphere.To inhibit possible oxygen vacancies during the thermal step, theoxidizing atmosphere is preferably used. To inhibit a possible increasein film thickness resulting from the heat treatment, the inert gasatmosphere is preferably used.

The temperature of the heat treatment after the formation of a hafniumaluminium oxide film is preferably at least 900° C. as already shown inFIG. 31. A heat treatment temperature of at least 900° C. enablesetching resistance to be significantly improved. This makes it possibleto inhibit a possible variation in the amount of side etching of thehigh dielectric constant insulating film and a possible variation in thecoupling ratio (C2/(C1+C2)) of the memory cell. Further, the large sideetching amount of the high dielectric constant insulating film increasesthe amount of high electric field leakage, degrading theprogramming/erasing characteristic of the memory cell. The above hightemperature thermal process enables the etching resistance to besignificantly improved, allowing the prevention of the above problems.

In the above second and third embodiments, a very thin silicon oxidefilm may be formed on at least one of the bottom surface of the lowersilicon nitride film 204 and the top surface of the upper siliconnitride film 205. In this case, the film thickness of the very thinsilicon oxide film is desirably small but enough to minimize theformation of a bird's beak. For example, the film thickness of thesilicon oxide film is desirably smaller than 1 nm. The formation of sucha silicon oxide film makes it possible to provide a favorable interfacebetween the lower silicon nitride film 204 and the floating gateelectrode 13 and between the upper silicon nitride film 205 and thecontrol electrode 21. This is because the formation of a silicon oxidefilm between the silicon nitride film and the polycrystalline siliconelectrode enables a reduction in interface state and allows theinhibition of a flat band voltage shift caused by fixed chargeattributed to the silicon nitride film. The favorable interface formedreduces low electric field leakage, allowing the charge retentioncharacteristic of the element to be improved.

Further, in the above first and third embodiments, the lower siliconoxide film 201 and upper silicon oxide film 203 may be formed of siliconoxinitride films containing nitrogen. In the above second and thirdembodiments, the lower silicon nitride film 204 and upper siliconnitride film 205 may be formed of silicon oxinitride films containingoxygen.

Embodiment 4

A fourth embodiment of the present invention will be described below.The matters described in the first to third embodiments will not bedescribed in detail.

The present embodiment corresponds to any of the configurations of thefirst to third embodiments in which the high dielectric constantinsulating film 202 contains carbon. Specifically, carbon is introduced,by ion implantation, into the high dielectric constant insulating film202 formed. At this time, dose and acceleration energy are adjusted sothat the concentration of carbon in the high dielectric constantinsulating film 202 is at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³. Any method other than ion implantation may be used providedthat the concentration of carbon in the high dielectric constantinsulating film 202 can be controlled to the above values.

When the concentration of carbon in the high dielectric constantinsulating film 202 is at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³ as described above, the insulating property of the highdielectric constant insulating film is inhibited from being degradedwhen silicon oxide films or silicon nitride films are formed. Aconstituent element of the high dielectric constant insulating film suchas oxygen may be detached from the film owing to a reducing atmospherecontaining hydrogen, a halogen atmosphere containing chlorine, or hightemperature annealing; the reducing atmosphere and halogen atmosphereare used to form silicon oxide films and silicon nitride films. Thecontainment of carbon is expected to inhibit the possible detachment ofthe constituent element and the possible degradation of the insultingproperty of the high dielectric constant insulating film.

FIG. 17 is a diagram showing the relationship between the concentrationof carbon in the high dielectric constant insulating film and theleakage current density. Although hafnium aluminate (HfAlO) is used forthe high dielectric constant insulating film, similar characteristicsare obtained by using aluminium oxide (alumina: Al₂O₃). Samples formeasurement were obtained by introducing carbon into the high dielectricconstant insulating film by ion implantation and performing heattreatment at 1,050° C. FIG. 17 shows that the leakage current increasesrapidly when the concentration of carbon in the high dielectric constantinsulating film exceeds 2×10²² atoms/cm³.

FIG. 18 is a diagram showing the relationship between the concentrationof carbon in the high dielectric constant insulating film and theetching rate of the high dielectric constant insulating film based onRIE. FIG. 18 shows that the etching rate increases rapidly when theconcentration of carbon in the high dielectric constant insulating filmis at least 1×10¹⁹ atoms/cm³. This is because the containment of carbonin the high dielectric constant insulating film at the above describedconcentration reduces the film density and increases the RIE rate.

As described above, measurements in FIGS. 17 and 18 also indicate thatthe concentration of carbon in the high dielectric constant insulatingfilm 202 is desirably at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³.

Further, if the high dielectric constant insulating film containshafnium, its melting point is increased, which preventing the insulatingproperty of the inter-electrode insulating film from being degraded inhigh temperature steps.

The containment of carbon in the entire high dielectric constantinsulating film within the above concentration range makes the effectsof the present embodiment significant. However, even the containment ofcarbon in part of the high dielectric constant insulating film withinthe above concentration range allows certain effects to be exerted.

Furthermore, the formation of a high dielectric constant insulating filmby sputtering enables a sufficient reduction in the concentration ofcarbon in the high dielectric constant insulating film. This makes itpossible to precisely control the concentration of carbon in the finalhigh dielectric constant insulating film.

Embodiment 5

A fifth embodiment of the present invention will be described below. Thematters described in the first to third embodiments will not bedescribed in detail.

The present embodiment corresponds to any of the configurations of thefirst to third embodiments in which the high dielectric constantinsulating film 202 contains nitrogen. Specifically, nitrogen isintroduced, by ion implantation, into the high dielectric constantinsulating film 202 formed. At this time, dose and acceleration energyare adjusted so that the concentration of nitrogen in the highdielectric constant insulating film 202 is at least 1×10¹⁹ atoms/cm³ andat most 2×10²² atoms/cm³. Any method other than ion implantation may beused provided that the concentration of nitrogen in the high dielectricconstant insulating film 202 can be controlled to the above values.

When the concentration of nitrogen in the high dielectric constantinsulating film 202 is at least 1×10¹⁹ atoms/cm³ and at most 2×10²²atoms/cm³ as described above, the insulating property of the highdielectric constant insulating film is inhibited from being degradedwhen silicon oxide films or silicon nitride films are formed. Aconstituent element of the high dielectric constant insulating film suchas oxygen may be detached from the film owing to a reducing atmospherecontaining hydrogen, a halogen atmosphere containing chlorine, or hightemperature annealing; the reducing atmosphere and halogen atmosphereare used to form silicon oxide films and silicon nitride films. Thecontainment of nitrogen is expected to inhibit the possible detachmentof the constituent element and the possible degradation of the insultingproperty of the high dielectric constant insulating film.

FIG. 19 is a diagram showing the relationship between the concentrationof nitrogen in the high dielectric constant insulating film and theleakage current density. Although hafnium aluminate (HfAlO) is used forthe high dielectric constant insulating film, similar characteristicsare obtained by using aluminium oxide (alumina: Al₂O₃). Samples formeasurement were obtained by introducing nitrogen into the highdielectric constant insulating film by ion implantation. FIG. 19 showsthat the leakage current can be inhibited when the concentration ofnitrogen in the high dielectric constant insulating film is at least1×10¹⁹ atoms/cm³ and at most 2×10²² atoms/cm³. This is because settingthe concentration of nitrogen in the high dielectric constant insulatingfilm within the above range makes it possible to effectively inhibit thedetachment of a constituent element of the high dielectric constantinsulating film such as oxygen.

FIG. 20 is a diagram showing the measurement of the distribution of theconcentration of aluminium (Al) in a depth direction. Although hafniumaluminate (HfAlO) is used for the high dielectric constant insulatingfilm, similar characteristics are obtained by using aluminium oxide(alumina: Al₂O₃). Samples for measurement were obtained by forming asilicon oxide film on a silicon substrate, forming a high dielectricconstant insulating film, and performing heat treatment at 1,000° C. for10 seconds. SIMS analysis was used for the measurement. FIG. 20 showsthat when the concentration of nitrogen in the high dielectric constantinsulating film is lower than 1×10¹⁹ atoms/cm³, Al in the HfAlO filmdiffuses significantly into the silicon oxide film (SiO₂ film). Thismarkedly varies the Hf/Al ratio of the HfAlO film. In contrast, at anitrogen concentration of 1×10¹⁹ atoms/cm³, Al in the HfAlO film doesnot virtually diffuse into the silicon oxide film. Consequently, settingthe concentration of nitrogen in the high dielectric constant insulatingfilm equal to or greater than 1×10¹⁹ atoms/cm³ enables the Hf/Al ratioof the HfAlO film to be adequately controlled.

The containment of nitrogen in the entire high dielectric constantinsulating film within the above concentration range makes the effectsof the present embodiment significant. However, even the containment ofnitrogen in part of the high dielectric constant insulating film withinthe above concentration range allows certain effects to be exerted.

Furthermore, the formation of a high dielectric constant insulating filmby sputtering enables a sufficient reduction in the concentration ofnitrogen in the resulting high dielectric constant insulating film. Thismakes it possible to precisely control the concentration of nitrogen inthe final high dielectric constant insulating film.

Embodiment 6

A sixth embodiment of the present invention will be described below. Thematters described in the first to third embodiments will not bedescribed in detail.

The present embodiment corresponds to any of the configurations of thefirst to third embodiments in which the high dielectric constantinsulating film 202 contains hydrogen. Specifically, hydrogen isintroduced into the formed high dielectric constant insulating film 202by heat-treating it in a hydrogen gas atmosphere at 100 to 550° C. Atthis time, heat treatment temperature, heat treatment time, and hydrogengas partial pressure are adjusted so that the concentration of hydrogenin the high dielectric constant insulating film 202 is at least 1×10¹⁹atoms/cm³ and at most 5×10²² atoms/cm³. Any method other than the heattreatment in the hydrogen atmosphere may be used provided that theconcentration of hydrogen in the high dielectric constant insulatingfilm 202 can be controlled to the above values.

When the concentration of hydrogen in the high dielectric constantinsulating film 202 is at least 1×10¹⁹ atoms/cm³ and at most 5×10²²atoms/cm³ as described above, a sufficient amount of hydrogen can besupplied to the silicon oxide films 201 and 203, the silicon nitridefilms 204 and 205, and the interface of the insulating film contained inthe inter-electrode insulating film of the stack structure, during thehigh temperature step in manufacturing process. This improves theinsulating property of the inter-electrode insulating film.

FIG. 21 is a diagram showing the relationship between the concentrationof hydrogen in the high dielectric constant insulating film and theleakage current density. Although hafnium aluminate (HfAlO) is used forthe high dielectric constant insulating film, similar characteristicsare obtained by using aluminium oxide (alumina: Al₂O₃). Samples formeasurement were obtained by heat-treating the formed high dielectricconstant insulating film in a hydrogen gas atmosphere. FIG. 21 showsthat the leakage current can be inhibited when the concentration ofhydrogen in the high dielectric constant insulating film is at least1×10¹⁹ atoms/cm³ and at most 5×10²² atoms/cm³. This is because settingthe concentration of hydrogen in the high dielectric constant insulatingfilm within the above range makes it possible to supply a sufficientamount of hydrogen to the silicon oxide films and silicon nitride filmsand to effectively terminate the interface level at hydrogen. A hydrogenconcentration of higher than 5×10²² atoms/cm³ reduces the film densityand degrades the insulating property, increasing the amount of leakagecurrent.

FIG. 22 is a diagram showing measurements of electric capacitance. FIG.22 shows that the interface level increases when the concentration ofhydrogen in the high dielectric constant insulating film is lower than1×10¹⁹ atoms/cm³.

The containment of hydrogen in the entire high dielectric constantinsulating film within the above concentration range makes the effectsof the present embodiment significant. However, even the containment ofhydrogen in part of the high dielectric constant insulating film withinthe above concentration range allows certain effects to be exerted.

Furthermore, the formation of a high dielectric constant insulating filmby sputtering enables a sufficient reduction in the concentration ofhydrogen in the resulting high dielectric constant insulating film. Thismakes it possible to precisely control the concentration of hydrogen inthe final high dielectric constant insulating film.

Embodiment 7

A seventh embodiment of the present invention will be described below.The matters described in the above embodiments will not be described indetail.

In the present embodiment, a high dielectric constant insulating film202 containing carbon, nitrogen, or hydrogen is formed by CVD or ALDusing a source gas containing carbon, nitrogen, or hydrogen. Theconcentration of carbon, nitrogen, or hydrogen in the high dielectricconstant insulating film 202 is as described above in the fourth tosixth embodiments. The concentration of the element can be appropriatelycontrolled on the basis of the type or partial pressure of the sourcegas or the film formation temperature.

For example, any of the source gases listed below is used to form ahafnium aluminate (HfAlO) as a high dielectric constant insulating film.

Examples of hafnium source gas include tetrakis dimethyl amino hafnium(Hf[N(CH₃)₂]₄), tetrakis diethyl amino hafnium (Hf[N(C₂H₅)₂]₄), tetrakisethylmethyl amino hafnium (Hf[N(C₂H₅)(CH₃)]₄), tetra methoxy hafnium(Hf(OCH₃)₄), tetra-1-propoxy hafnium (Hf(O-i-C₃H₇)₄), andtetrakis(dipivaloylmethanato)hafnium (Hf(C₁₁H₁₉O₂)₄). Examples ofaluminium source gas include trimethyl aluminium (Al(CH₃)₃), triethylaluminium (Al(C₂H₅)₃), tris(sec-butoxy)aluminium (Al(O-sec-C₄H₉)₃),tri-methoxy aluminium (Al(OCH₃)₃), and tri-ethoxy aluminium(Al(OC₂H₅)₃). Examples of oxygen source gas include oxygen gas, ozone,steam (water vapor), and oxygen radicals.

Any of these source gases allows at least one of carbon, nitrogen, andhydrogen to be added to the high dielectric constant insulating filmduring the film forming process. Selection of an appropriate source gasallows carbon, nitrogen, and hydrogen to be simultaneously added.Selection of an appropriate source gas and appropriate film formationconditions allows carbon, nitrogen, and hydrogen to be simultaneouslyadded at the above desirable element concentrations.

Embodiment 8

An eighth embodiment of the present invention will be described below.The matters described in the above embodiments will not be described indetail.

FIG. 23 is a sectional view schematically showing the detailedconfiguration of a nonvolatile semiconductor memory device in accordancewith the present embodiment in the word line direction (channel widthdirection). Components corresponding to those shown in FIGS. 1A and 1Bto 5A and 5B are denoted by the same reference numerals and will not bedescribed in detail.

In the present embodiment, the inter-electrode insulating film 20 has afirst portion 20 a formed along the top surface of the floating gateelectrode 13, a second portion 20 b formed along the side surfaces ofthe floating gate electrode 13, and a third portion 20 c formed betweenthe adjacent floating gate electrodes 13. The third portion 20 c has alower oxygen concentration than the first portion 20 a.

Thus, in the present embodiment, the third portion 20 c, formed betweenthe adjacent floating gate electrodes 13, has a lower oxygenconcentration. The third portion 20 c, having the lower oxygenconcentration, offers a reduced dielectric constant. This reduces theparasitic capacitance between the adjacent floating gate electrodes 13,allowing possible memory malfunctions to be avoided. On the other hand,the first portion 20 a, formed along the top surface of the floatinggate electrode 13, has a higher oxygen concentration and can thusprovide a large electric capacitance desirable for the inter-electrodeinsulating film. Therefore, nonvolatile semiconductor memory devicehaving excellent characteristic and reliability can be obtained.

In the present embodiment, the inter-electrode insulating film 20 mayhave such a stack structure as shown in any of the first to thirdembodiments or a single layer structure formed of the high dielectricconstant insulating film. The above effects can be exerted regardless ofwhether the inter-electrode insulating film 20 has a stack structurecontaining the high dielectric constant insulating film or a singlelayer structure formed of the high dielectric constant insulating film.

The structure of the above present embodiment is obtained by forming ahigh dielectric constant insulating film by means of CVD or ALD usingozone or oxygen radicals as oxygen source gas. That is, the narrowgroove between the adjacent floating gate electrodes 13 inactivatesozone or oxygen radicals, which have a short lifetime. This reduces theozone or oxygen radicals reaching the surface of the isolationinsulating film 17. On the other hand, ozone or oxygen radicals arelikely to reach the top surface of the floating gate electrode 13 owingto its projection. This makes it possible to provide the structure ofthe above present embodiment.

Further, as shown in FIG. 24, after a high dielectric constantinsulating film is formed as the inter-electrode insulating film 20,oxygen may be introduced into the high dielectric constant insulatingfilm by oblique ion implantation. This method also makes it possible toprovide the structure of the above present embodiment. In this case, theoxygen concentration is high in the first portion 20 a, extending alongthe top surface of the floating gate electrode 13, and low in the thirdportion 20 c, extending along the top surface of the isolationinsulating film 17. The oxygen concentration in the second portion 20 b,extending along the side surfaces of the floating gate electrode 13, isintermediate between that in the first portion 20 a and that in thethird portion 20 c.

Embodiment 9

A ninth embodiment of the present invention will be described below. Thematters described in the above embodiments will not be described indetail.

In the present embodiment, the inter-electrode insulating film 20 isformed of the lower silicon oxide film 201, high dielectric constantinsulating film 202, and upper silicon oxide film 203 as is the casewith the first embodiment. However, in the present embodiment, at leastone of the lower silicon oxide film 201 and upper silicon oxide film 203contains at least one of carbon, nitrogen, and chlorine at a peakconcentration of at least 1×10¹⁹ atoms/cm³.

The high dielectric constant insulating film 202 formed by normal CVD orALD contains an impurity element (carbon, nitrogen, or chlorine)contained in the source gas, for example, at a peak concentration of atleast 1×10¹⁹ atoms/cm³. For example, during the formation of a highdielectric constant insulating film 202 by deposition, the use of anorganic metal material as source gas allows the resulting highdielectric constant insulating film 202 to contain carbon. The use ofsource gas containing nitrogen allows the resulting high dielectricconstant insulating film 202 to contain nitrogen. The use of source gascontaining chlorine allows the resulting high dielectric constantinsulating film 202 to contain chlorine. In forming a stack film of thelower silicon oxide film 201, high dielectric constant insulating film202, and upper silicon oxide film 203, impurities the same as thosecontained in the high dielectric constant insulating film 202 are dopedinto at least one of the lower silicon oxide film 201 and upper siliconoxide film 203 at a peak concentration of at least 1×10¹⁹ atoms/cm³.This makes it possible to inhibit the impurities from diffusing betweenthe lower silicon oxide film 201 and the high dielectric constantinsulating film 202 and the upper silicon oxide film 203. In particular,the impurities are inhibited from diffusing from the high dielectricconstant insulating film 202 to the lower silicon oxide film 201 andupper silicon oxide film 203. This makes it possible to drasticallyimprove the thermostability of the stack film of the lower silicon oxidefilm 201, high dielectric constant insulating film 202, and uppersilicon oxide film 203. As a result, an inter-electrode insulating filmwith an excellent insulating property can be provided.

In addition to exerting the above effect, the present embodiment canproduce effects described below by doping the respective impurityelements.

When at least one of the lower silicon oxide film 201 and upper siliconoxide film 203 contains nitrogen, its thermostability is drasticallyimproved. This makes it possible to significantly improve the insulatingproperty of the stack structure of the lower silicon oxide film 201,high dielectric constant insulating film 202, and upper silicon oxidefilm 203. Further, when nitrogen is contained in the lower silicon oxidefilm 201 or upper silicon oxide film 203, the lower silicon oxide film201 or upper silicon oxide film 203 serves as a diffusion source fornitrogen. The subsequent high temperature thermal step of themanufacturing process diffuses the nitrogen into the high dielectricconstant insulating film 202. This enables the thermostability of thehigh dielectric constant insulating film 202 to be improved. Moreover,when a high dielectric constant insulating film 202 is formed of anoxide, the dielectric constant of the high dielectric constantinsulating film 202 increases.

When at least one of the lower silicon oxide film 201 and upper siliconoxide film 203 contains chlorine, the gettering effect of chlorine isexerted. This makes it possible to inhibit the disadvantageous, possiblediffusion of the metal element constituting the high dielectric constantinsulating film 202 into the tunnel insulating film 12 through thefloating gate electrode 13, degrading the film quality of the tunnelinsulating film 12. Even if the metal element constituting the highdielectric constant insulating film 202 diffuses into the lower siliconoxide film 201 or upper silicon oxide film 203, the gettering effect ofchlorine enables the metal element to be electrically inactivated. Thismakes it possible to inhibit the possible degradation of the insulatingproperty of the lower silicon oxide film 201 and upper silicon oxidefilm 203.

FIG. 25 is a diagram showing the relationship between the concentrationof chlorine (Cl) in the silicon oxide film and the yield of the tunnelinsulating film. The chlorine concentration was measured by SIMS. Theyield indicates the rate of cells with the tunnel insulating filmprevented from being broken down after one hundred thousand programmingoperations. As is apparent from FIG. 25, at least 1×10¹⁹ atoms/cm³ ofchlorine in the silicon oxide film allows the yield of the tunnelinsulating film to be drastically improved.

If at least one of the lower silicon oxide film 201 and upper siliconoxide film 203 contains carbon, carbon can be fed from the silicon oxidefilm to the high dielectric constant insulating film 202. This enablesthe charge trap level in the high dielectric constant insulating film202 to be terminated, allowing the high dielectric constant insulatingfilm 202 to be improved.

FIG. 26 is a diagram showing the relationship between the concentrationof carbon (C) in the silicon oxide film and a variation in the threshold(Vth) for the memory cell caused by detrapping of charge from theinter-electrode insulating film. The carbon concentration on the axis ofabscissa was measured by SIMS. The axis of ordinate indicates the amountof variation in a threshold for a programmed cell after 10 years, thevariation being caused by detrapping of charge from the inter-electrodeinsulating film. As shown in FIG. 26, 1×10¹⁹ atoms/cm³ of carbon in thesilicon oxide film enables a trap site in the high dielectric constantinsulating film to be terminated with carbon. The variation in thresholdcan thus be sharply reduced.

Impurities can be doped into the lower silicon oxide film 201 or uppersilicon oxide film 203, for example, as described below.

Silicon oxide films are formed by CVD using dichlorosilane and nitrousoxide as source gas at least 700° C. and at most 900° C. This allowsdesired concentrations of nitrogen and chlorine to be contained in thesilicon oxide films 201 and 203. Further, desired concentrations ofnitrogen and carbon can be contained in the silicon oxide films 201 and203 by forming the silicon oxide film by means of ALD using TDMAS andozone gas as source gas at least 300° C. and at most 700° C.Alternatively, after silicon oxide films are formed by CVD usingdisilane and oxygen as source gas at least 700° C. and at most 900° C.,nitrogen, chlorine, or carbon may be introduced into the silicon oxidefilms by ion implantation. Alternatively, after silicon oxide films areformed by sputtering in an atmosphere containing oxygen using silicon ora silicon oxide as a target material, nitrogen, chlorine, or carbon maybe introduced into the silicon oxide films by ion implantation.

In the description of the present embodiment, the inter-electrodeinsulating film 20 is formed of the lower silicon oxide film 201, highdielectric constant insulating film 202, and upper silicon oxide film203, as is the case with the first embodiment. However, the aboveconfiguration with doped nitrogen, chlorine, or carbon is applicable tothe case where the inter-electrode insulating film 20 is formed of thelower silicon nitride film 204, lower silicon oxide film 201, highdielectric constant insulating film 202, upper silicon oxide film 203,and upper silicon nitride film 205, as is the case with the thirdembodiment. That is, also in this case, effects similar to thosedescribed above can be exerted provided that at least one of the lowersilicon oxide film 201 and upper silicon oxide film 203 contains atleast one of carbon, nitrogen, and chlorine at a peak concentration ofat least 1×10¹⁹ atoms/cm³.

Embodiment 10

A tenth embodiment of the present invention will be described below. Thepresent embodiment relates to a semiconductor device of what is called aMONOS structure (nonvolatile semiconductor memory device). The mattersdescribed in the above embodiments will not be described in detail.

FIG. 27 is a sectional view showing the basic configuration of asemiconductor device (nonvolatile semiconductor memory device) inaccordance with the present embodiment in the bit line direction(channel length direction). The basic configuration and basicmanufacturing method in accordance with the present embodiment aresimilar to those shown in FIGS. 1A and 1B to 5A and 5B. Componentscorresponding to those shown in FIGS. 1A and 1B to 5A and 5B are denotedby the same reference numerals and will not be described in detail.

The impurity diffusion layer 24 for a source/drain area is provided in asurface area of the silicon substrate (semiconductor substrate) 11. Agate structure is provided on the channel area between the impuritydiffusion layers 24; the gate structure has a stack of the tunnelinsulating film (first insulating film) 12, charge storage layer 30,upper insulating film (second insulating film) 20, and control gateelectrode (control electrode) 21. The upper insulating film 20 is formedof a stack film of the lower silicon oxide film 201, high dielectricconstant insulating film (intermediate insulating film) 202, and uppersilicon oxide film 203.

When the stack film of the lower silicon oxide film 201, high dielectricconstant insulating film (intermediate insulating film) 202, and uppersilicon oxide film 203 is used as the upper insulating film 20 providedbetween the charge storage layer 30 and the control gate electrode 21 asdescribed above, a leakage current generated by applying a high electricfield for a programming operation or an erasing operation is reduced,increasing the speed of the element. This also drastically improves thebreakdown voltage, providing a sufficient memory operation speed. Theuse of the stack film also reduces the leakage current of the upperinsulating film 20 during the application of a low electric field of atmost about 10 MV/cm, offering a sufficient memory retentioncharacteristic. This further sharply reduces the trapped charge andsuppresses the emission of the trapped charge, making it possible toavoid memory malfunctions caused by a variation in the threshold for thememory cell.

Forming a stack film including the high dielectric constant insulatingfilm 202 as the upper insulating film 20 enables an increase in physicalfilm thickness without the need to increase electrical film thickness.This makes it possible to reduce the leakage current during theapplication of a high electric field, while increasing the breakdownvoltage. Further, providing the silicon oxide films 201 and 203, havinga larger barrier height than the high dielectric constant insulatingfilm 202, enables an effective reduction in the leakage current duringthe application of a low electric field to the upper insulating film 20for memory retention or the like. Furthermore, providing the uppersilicon oxide film 203 enables the prevention of possible formation ofoxygen vacancies in the high dielectric constant insulating film 202 asa result of a reducing atmosphere (for example, a silane (SiH₄) gasatmosphere) used to form a control gate electrode 21. A reduction inoxygen vacancies in the high dielectric constant insulating film 202enables the inhibition of a possible increase in leakage current and apossible decrease in breakdown voltage. Further, providing the siliconoxide films 201 and 203 enables the supply of oxygen to oxygen vacanciesproduced during the formation of a high dielectric constant insulatingfilm 202 and during the subsequent steps. Thus, the oxygen vacancies canbe reduced. Moreover, providing the silicon oxide films 201 and 203having high barrier height reduces the charge (trapped charge) trappedby the high dielectric constant insulating film 202 during aprogramming/erasing operation. This also suppresses the emission of thetrapped charge toward the control gate electrode 21. This excellent trapcharacteristic enables a reduction in variation in the threshold for thememory cell.

Description will be given of a method for manufacturing a nonvolatilesemiconductor memory device in accordance with the present embodiment.

First, an element formation area and an isolation area are formed in thesilicon substrate 11 using an ordinary method. A tunnel insulating film12 of thickness 2 to 5 nm is subsequently formed on the surface of thesilicon substrate 11 by thermal oxidation. A silicon nitride film ofthickness 5 to 20 nm is subsequently formed which constitutes the chargestorage layer 30. A lower silicon oxide film 201 of thickness about 1 to5 nm is formed on the surface of the silicon nitride film 30 by CVD. Ahafnium aluminate (HfAlO) film as the high dielectric constantinsulating film 202 is subsequently formed by ALD on the surface of thelower silicon oxide film 201 to a thickness of between a value equal tothe thickness of one atomic layer and about 5 nm. An upper silicon oxidefilm 203 of thickness about 1 to 5 nm is formed on the surface of thehafnium aluminate film 202 by CVD. A control gate electrode film 21 issubsequently formed on the upper insulating film 20 formed of the lowersilicon oxide film 201, high dielectric constant insulating film 202,and upper silicon oxide film 203. Further, a mask film 22 is formed onthe control gate electrode film 21 by CVD.

Then, the mask film 22, control gate electrode film 21, upper insulatingfilm 20, charge storage layer 30, and tunnel insulating film 12 aresequentially etched by RIE through a resist mask (not shown). Impuritiesare subsequently implanted into the silicon substrate 11 by ionimplantation to form an impurity diffusion layer 24 for source/drain.

An interlayer insulating film 25 is then formed by CVD or the like.Further, a wiring layer or the like (not shown) is formed using awell-known technique. A nonvolatile semiconductor memory device with aMONOS structure is thus obtained.

With the above manufacturing method, the lower silicon oxide film 201and upper silicon oxide film 203 are formed by CVD. However, a methodsuch as ALD, sputtering, or a radical process (formation of a lowersilicon oxide film) may be used.

Further, with the above manufacturing method, the high dielectricconstant insulating film 202 is formed by ALD. However, a method such asCVD or sputtering may be used. The present manufacturing methoddesirably uses ALD in order to ensure a uniform film thickness and toinhibit a variation in characteristics among the memory cells.

Furthermore, in the present embodiment, the upper insulating film 20 isformed of the lower silicon oxide film 201, high dielectric constantinsulating film 202, and upper silicon oxide film 203 as is the casewith the first embodiment. However, the structure in accordance with thepresent embodiment is also applicable to the case where the upperinsulating film 20 is formed of the lower silicon nitride film 204, highdielectric constant insulating film 202, and upper silicon nitride film205 as is the case with the second embodiment. The structure inaccordance with the present embodiment is also applicable to the casewhere the upper insulating film 20 is formed of the lower siliconnitride film 204, lower silicon oxide film 201, high dielectric constantinsulating film 202, upper silicon oxide film 203, and upper siliconnitride film 205 as is the case with the third embodiment.

Embodiment 11

An eleventh embodiment of the present invention will be described below.The matters described in the above embodiments will not be described indetail.

FIGS. 34 and 35 are sectional views schematically showing a part of amethod for manufacturing a nonvolatile semiconductor memory device inaccordance with the present embodiment in the word line direction(channel width direction). Components corresponding to those shown inFIGS. 1A and 1B to 5A and 5B are denoted by the same reference numeralsand will not be described in detail.

After the steps shown in FIGS. 3A and 3B, a silicon film 31 of thicknessabout 0.8 mm is formed by CVD on the exposed surfaces of thepolycrystalline silicon film (floating gate electrode film) 13 and thesilicon oxide film (isolation insulating film) 17. Specifically, silane(SiH₄) gas is used to form a silicon film 31 at 550° C.

Then, as shown in FIG. 35, the silicon film 31 is nitrided to form asilicon nitride film 32. Specifically, a radical nitriding process isexecuted at 400° C. for 60 seconds in an atmosphere containing nitrogengas with a partial pressure of 10 Pa. This allows the silicon film 31 tobe completely nitrided to form a silicon nitride film 32. Thus, aninter-electrode insulating film 20 formed of the silicon nitride film 32is obtained. The subsequent steps are similar to those shown in FIGS. 1Aand 1B to 5A and 5B.

Thus, in the present embodiment, the silicon film 31 is first formed onthe floating gate electrode film 13 and isolation insulating film 17 andthen nitrided to form a silicon nitride film 32. This allows ahigh-quality silicon nitride film 32 to be reliably formed. If anitriding process was executed without forming a silicon film 31, ahigh-quality silicon nitride film might be formed on the floating gateelectrode film 13 formed of the polycrystalline silicon film but not onthe isolation insulating film 17 formed of the silicon oxide film.According to the present embodiment, the silicon film 31 is formed andthen nitrided to form a silicon nitride film 32. This enables ahigh-quality silicon nitride film 32 to be also formed on the isolationinsulating film 17.

Further, the ability to form a high-quality silicon nitride film 32improves the barrier property of the silicon nitride film 32 on theisolation insulating film 17. Thus, a heat treatment in an oxidizingatmosphere during the subsequent step makes it possible to preventoxidizing gas from entering the isolation insulating film 17. Thus, theoxidizing gas can be inhibited from diffusing to the tunnel insulatingfilm 12 via the isolation insulating film 17. This enables theprevention of possible oxidation of a bird's beak of the tunnelinsulating film 12. As a result, the programming/erasing characteristicof the memory cell can be improved. Further, a high-quality siliconnitride film 32 undergoing reduced defects is formed, allowing areduction in the leakage current flowing between the adjacent memorycells.

FIGS. 36A, 36B and 36C are diagrams showing the programmingcharacteristic of the memory cell. The axis of abscissa indicatesprogram time. The axis of ordinate indicates the threshold voltage Vthfor the memory cell. The programming voltage is 17, 18, 19, or 20V. FIG.36A shows that the film thickness t of the silicon film 31 is 0 nm (thesilicon film 31 is not formed). FIG. 36B shows that the film thickness tof the silicon film 31 is 0.4 nm. FIG. 36C shows that the film thicknesst of the silicon film 31 is 0.8 nm. The results shown in FIGS. 36A, 36B,and 36C indicate that the program time decreases and the width of awindow for the programming voltage increases, with increasing filmthickness t of the silicon film 31. This is because improved oxidationresistance enables the coupling ratio of the memory cell to beoptimized. Therefore, setting the film thickness of the silicon film 31at about 0.8 nm provides a high-quality silicon nitride film 32 with animproved barrier property.

In the present embodiment, the inter-electrode insulating film 20 mayhave a single layer structure formed of the silicon nitride film 32 orsuch a stack structure as shown in the second and third embodiments.That is, the inter-electrode insulating film 20 may be formed of thelower silicon nitride film 204, high dielectric constant insulating film(intermediate insulating film) 202, and upper silicon nitride film 205as shown in FIGS. 14A and 14B for the second embodiment. Alternatively,the inter-electrode insulating film 20 may be formed of the lowersilicon nitride film 204, lower silicon oxide film 201, high dielectricconstant insulating film (intermediate insulating film) 202, uppersilicon oxide film 203, and upper silicon nitride film 205 as shown inFIGS. 16A and 16B for the third embodiment. In any case, the method inaccordance with the present embodiment is applicable to the formation ofa lower silicon nitride film 204.

Embodiment 12

A twelfth embodiment of the present invention will be described below.The matters described in the above embodiments will not be described indetail.

FIG. 37 is a sectional view schematically showing a part of a method formanufacturing a nonvolatile semiconductor memory device in accordancewith the present embodiment in the word line direction (channel widthdirection). Components corresponding to those shown in FIGS. 1A and 1Bto 5A and 5B are denoted by the same reference numerals and will not bedescribed in detail.

After the steps shown in FIGS. 3A and 3B, a silicon nitride film 32 isformed by ALD on the exposed surfaces of the polycrystalline siliconfilm (floating gate electrode film) 13 and the silicon oxide film(isolation insulating film) 17. Specifically, dichlorosilane is used asa silicon source, and an ammonia radical is used as a nitriding agent.The film formation temperature is set at about 450° C. During theformation of a silicon nitride film by ALD, the step of forming asilicon layer and the step of nitriding the silicon layer are repeated anumber of times. The method in accordance with the present embodimentfirst executes the step of forming a silicon layer.

Thus, in the present embodiment, to form a silicon nitride film 32 byALD, a silicon layer is first formed on the floating gate electrode film13 and isolation insulating film 17 and then nitrided. This allows ahigh-quality silicon nitride film 32 to be reliably formed on thefloating gate electrode film 13 and isolation insulating film 17 as isthe case with the eleventh embodiment.

Further, the pre-formation of a silicon layer makes it possible toprevent ammonia, a nitriding agent, from entering the isolationinsulating film 17. This enables the prevention of possible degradationof the tunnel insulating film 12, providing memory cells with excellentcharacteristics.

FIG. 38 is a diagram showing the relationship between the film formationtemperature of the silicon nitride film 32 and the concentration ofhydrogen in the isolation insulating film 17. FIG. 39 is a diagramshowing the relationship between the film formation temperature of thesilicon nitride film 32 and a leakage current generated by applying anelectric field of 5 MV/cm to the inter-electrode insulating film. FIG.38 shows that a film formation temperature of higher than about 450° C.increases the concentration of hydrogen in the isolation insulating film17. FIG. 39 shows that a film formation temperature of lower than about350° C. increases the magnitude of the leakage current. Therefore, thefilm formation temperature of the silicon nitride film 32 is preferablybetween 350° C. and 450° C.

The present embodiment uses the ammonia radical as a nitriding agent.However, a nitrogen radical may also be used. Also in this case, thepre-formation of a silicon layer prevents the surface of the isolationinsulating film 17 from being exposed directly to the nitrogen radical.This enables a reduction in the leakage current flowing between theadjacent memory cells.

In the present embodiment, the inter-electrode insulating film 20 mayhave a single layer structure formed of the silicon nitride film 32 orsuch a stack structure as shown in the second and third embodiments.That is, the inter-electrode insulating film 20 may be formed of thelower silicon nitride film 204, high dielectric constant insulating film(intermediate insulating film) 202, and upper silicon nitride film 205as shown in FIGS. 14A and 14B for the second embodiment. Alternatively,the inter-electrode insulating film 20 may be formed of the lowersilicon nitride film 204, lower silicon oxide film 201, high dielectricconstant insulating film (intermediate insulating film) 202, uppersilicon oxide film 203, and upper silicon nitride film 205 as shown inFIGS. 16A and 16B for the third embodiment. In any case, the method inaccordance with the present embodiment is applicable to the formation ofa lower silicon nitride film 204.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1. A semiconductor device comprising: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film including a lowersilicon nitride film, a lower silicon oxide film formed on the lowersilicon nitride film, an intermediate insulating film formed on thelower silicon oxide film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, an upper silicon oxide film formed on the intermediateinsulating film, and an upper silicon nitride film formed on the uppersilicon oxide film.
 2. A semiconductor device comprising: asemiconductor substrate; a first insulating film formed on thesemiconductor substrate; a charge storage layer formed on the firstinsulating film; a second insulating film formed on the charge storagelayer; and a control electrode formed on the second insulating film, thesecond insulating film having one of a first film structure, a secondfilm structure, and a third film structure, the first film structureincluding a lower silicon oxide film, an intermediate insulating filmformed on the lower silicon oxide film and containing a metal element,the intermediate insulating film having a relative dielectric constantof greater than 7, and an upper silicon oxide film formed on theintermediate insulating film, the second film structure including alower silicon nitride film, a lower silicon oxide film formed on thelower silicon nitride film, an intermediate insulating film formed onthe lower silicon oxide film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, an upper silicon oxide film formed on the intermediateinsulating film, and an upper silicon nitride film formed on the uppersilicon oxide film, the third film structure including a lower siliconnitride film, an intermediate insulating film formed on the lowersilicon nitride film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon nitride film formed on the intermediate insulatingfilm, the intermediate insulating film having a thickness equal to orgreater than that of one atomic layer and equal to or smaller than 5 nm.3. A semiconductor device comprising: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure and a second film structure, the first filmstructure including a lower silicon oxide film, an intermediateinsulating film formed on the lower silicon oxide film and containing ametal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon oxide filmformed on the intermediate insulating film, the second film structureincluding a lower silicon nitride film, a lower silicon oxide filmformed on the lower silicon nitride film, an intermediate insulatingfilm formed on the lower silicon oxide film and containing a metalelement, the intermediate insulating film having a relative dielectricconstant of greater than 7, an upper silicon oxide film formed on theintermediate insulating film, and an upper silicon nitride film formedon the upper silicon oxide film, the intermediate insulating film beingformed of a polycrystalline film, and crystal grains contained in thepolycrystalline film having an average grain size of at least 5 nm.
 4. Asemiconductor device comprising: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure, a second film structure, and a third filmstructure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, the third filmstructure including a lower silicon nitride film, an intermediateinsulating film formed on the lower silicon nitride film and containinga metal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon nitride filmformed on the intermediate insulating film, wherein the followingexpression is satisfied,T/(T+M+S)≧0.2 where T (T>0) is a concentration of a transition metalelement in the intermediate insulating film, M (M≧0) is a concentrationof a metal element other than the transition metal element in theintermediate insulating film, and S (S≧0) is a concentration of asemiconductor element in the intermediate insulating film.
 5. Asemiconductor device comprising: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure, a second film structure, and a third filmstructure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, the third filmstructure including a lower silicon nitride film, an intermediateinsulating film formed on the lower silicon nitride film and containinga metal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon nitride filmformed on the intermediate insulating film, the intermediate insulatingfilm having a carbon concentration of at least 1×10¹⁹ atoms/cm³ and atmost 2×10²² atoms/cm³.
 6. A semiconductor device comprising: asemiconductor substrate; a first insulating film formed on thesemiconductor substrate; a charge storage layer formed on the firstinsulating film; a second insulating film formed on the charge storagelayer; and a control electrode formed on the second insulating film, thesecond insulating film having one of a first film structure, a secondfilm structure, and a third film structure, the first film structureincluding a lower silicon oxide film, an intermediate insulating filmformed on the lower silicon oxide film and containing a metal element,the intermediate insulating film having a relative dielectric constantof greater than 7, and an upper silicon oxide film formed on theintermediate insulating film, the second film structure including alower silicon nitride film, a lower silicon oxide film formed on thelower silicon nitride film, an intermediate insulating film formed onthe lower silicon oxide film and containing a metal element, theintermediate insulating film having a relative dielectric constant ofgreater than 7, an upper silicon oxide film formed on the intermediateinsulating film, and an upper silicon nitride film formed on the uppersilicon oxide film, the third film structure including a lower siliconnitride film, an intermediate insulating film formed on the lowersilicon nitride film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon nitride film formed on the intermediate insulatingfilm, the intermediate insulating film having a nitrogen concentrationof at least 1×10¹⁹ atoms/cm³ and at most 2×10²² atoms/cm³.
 7. Asemiconductor device comprising: a semiconductor substrate; a firstinsulating film formed on the semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film having one of afirst film structure, a second film structure, and a third filmstructure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, the third filmstructure including a lower silicon nitride film, an intermediateinsulating film formed on the lower silicon nitride film and containinga metal element, the intermediate insulating film having a relativedielectric constant of greater than 7, and an upper silicon nitride filmformed on the intermediate insulating film, the intermediate insulatingfilm having a hydrogen concentration of at least 1×10¹⁹ atoms/cm³ and atmost 5×10²² atoms/cm³.
 8. A semiconductor device comprising: asemiconductor substrate; a first insulating film formed on thesemiconductor substrate; a charge storage layer formed on the firstinsulating film; a second insulating film formed on the charge storagelayer; and a control electrode formed on the second insulating film, thesecond insulating film having one of a first film structure and a secondfilm structure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, at least one of thelower silicon oxide film and the upper silicon oxide film being thickerthan the intermediate insulating film.
 9. A semiconductor devicecomprising: a semiconductor substrate; a first insulating film formed onthe semiconductor substrate; a charge storage layer formed on the firstinsulating film; a second insulating film formed on the charge storagelayer; and a control electrode formed on the second insulating film, thesecond insulating film having one of a first film structure and a secondfilm structure, the first film structure including a lower silicon oxidefilm, an intermediate insulating film formed on the lower silicon oxidefilm and containing a metal element, the intermediate insulating filmhaving a relative dielectric constant of greater than 7, and an uppersilicon oxide film formed on the intermediate insulating film, thesecond film structure including a lower silicon nitride film, a lowersilicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, at least one of thelower silicon oxide film and the upper silicon oxide film having acarbon concentration of at least 1×10¹⁹ atoms/cm³.
 10. A semiconductordevice comprising: a semiconductor substrate; a first insulating filmformed on the semiconductor substrate; a charge storage layer formed onthe first insulating film; a second insulating film formed on the chargestorage layer; and a control electrode formed on the second insulatingfilm, the second insulating film having one of a first film structureand a second film structure, the first film structure including a lowersilicon oxide film, an intermediate insulating film formed on the lowersilicon oxide film and containing a metal element, the intermediateinsulating film having a relative dielectric constant of greater than 7,and an upper silicon oxide film formed on the intermediate insulatingfilm, the second film structure including a lower silicon nitride film,a lower silicon oxide film formed on the lower silicon nitride film, anintermediate insulating film formed on the lower silicon oxide film andcontaining a metal element, the intermediate insulating film having arelative dielectric constant of greater than 7, an upper silicon oxidefilm formed on the intermediate insulating film, and an upper siliconnitride film formed on the upper silicon oxide film, at least one of thelower silicon oxide film and the upper silicon oxide film having achlorine concentration of at least 1×10¹⁹ atoms/cm³.
 11. A semiconductordevice having a plurality of memory cells each comprising: a firstinsulating film formed on a semiconductor substrate; a charge storagelayer formed on the first insulating film; a second insulating filmformed on the charge storage layer; and a control electrode formed onthe second insulating film, the second insulating film including a highdielectric constant insulating film containing a metal element andhaving a relative dielectric constant of greater than 7, the highdielectric constant insulating film having a first part formed along atop surface of the charge storage layer, a second part formed along aside surface of the charge storage layer, and a third part formedbetween the adjacent charge storage layers, the third part having alower oxygen concentration than the first part.
 12. A method formanufacturing a semiconductor device, the method comprising: forming afirst insulating film on a semiconductor substrate; forming a chargestorage layer on the first insulating film; forming a second insulatingfilm on the charge storage layer; and forming a control electrode filmon the second insulating film, forming the second insulating filmincluding one of forming a first film structure, forming a second filmstructure, and forming a third film structure, forming the first filmstructure including forming a lower silicon oxide film, forming anintermediate insulating film on the lower silicon oxide film, theintermediate insulating film containing a metal element and oxygen andhaving a relative dielectric constant of greater than 7, and forming anupper silicon oxide film on the intermediate insulating film; formingthe second film structure including forming a lower silicon nitridefilm, forming a lower silicon oxide film on the lower silicon nitridefilm, forming an intermediate insulating film on the lower silicon oxidefilm, the intermediate insulating film containing a metal element andoxygen and having a relative dielectric constant of greater than 7,forming an upper silicon oxide film on the intermediate insulating film,and forming an upper silicon nitride film on the upper silicon oxidefilm; forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and oxygen and having a relative dielectric constant ofgreater than 7, and forming an upper silicon nitride film on theintermediate insulating film, the intermediate insulating film beingformed by CVD or ALD using ozone or oxygen radicals as an oxygen source.13. A method for manufacturing a semiconductor device, the methodcomprising: forming a first insulating film on a semiconductorsubstrate; forming a charge storage layer on the first insulating film;forming a second insulating film on the charge storage layer; andforming a control electrode film on the second insulating film, formingthe second insulating film including one of forming a first filmstructure, forming a second film structure, and forming a third filmstructure, forming the first film structure including forming a lowersilicon oxide film, forming an intermediate insulating film on the lowersilicon oxide film, the intermediate insulating film containing a metalelement and oxygen and having a relative dielectric constant of greaterthan 7, and forming an upper silicon oxide film on the intermediateinsulating film; forming the second film structure including forming alower silicon nitride film, forming a lower silicon oxide film on thelower silicon nitride film, forming an intermediate insulating film onthe lower silicon oxide film, the intermediate insulating filmcontaining a metal element and oxygen and having a relative dielectricconstant of greater than 7, forming an upper silicon oxide film on theintermediate insulating film, and forming an upper silicon nitride filmon the upper silicon oxide film; forming the third film structureincluding forming a lower silicon nitride, forming an intermediateinsulating film on the lower silicon nitride film, the intermediateinsulating film containing a metal element and oxygen and having arelative dielectric constant of greater than 7, and forming an uppersilicon nitride film on the intermediate insulating film, theintermediate insulating film being formed by CVD or ALD using watervapor as an oxygen source.
 14. A method for manufacturing asemiconductor device, the method comprising: forming a first insulatingfilm on a semiconductor substrate; forming a charge storage layer on thefirst insulating film; forming a second insulating film on the chargestorage layer; and forming a control electrode film on the secondinsulating film, forming the second insulating film including one offorming a first film structure, forming a second film structure, andforming a third film structure, forming the first film structureincluding forming a lower silicon oxide film, forming an intermediateinsulating film on the lower silicon oxide film, the intermediateinsulating film containing a metal element and oxygen and having arelative dielectric constant of greater than 7, and forming an uppersilicon oxide film on the intermediate insulating film; forming thesecond film structure including forming a lower silicon nitride film,forming a lower silicon oxide film on the lower silicon nitride film,forming an intermediate insulating film on the lower silicon oxide film,the intermediate insulating film containing a metal element and oxygenand having a relative dielectric constant of greater than 7, forming anupper silicon oxide film on the intermediate insulating film, andforming an upper silicon nitride film on the upper silicon oxide film;forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and oxygen and having a relative dielectric constant ofgreater than 7, and forming an upper silicon nitride film on theintermediate insulating film, forming the second insulating filmincluding, after forming the intermediate insulating film, performing aheat treatment at a temperature higher than that at which theintermediate insulating film is formed.
 15. A method for manufacturing asemiconductor device, the method comprising: forming a first insulatingfilm on a semiconductor substrate; forming a charge storage layer on thefirst insulating film; forming a second insulating film on the chargestorage layer; and forming a control electrode film on the secondinsulating film, forming the second insulating film including one offorming a second film structure, and forming a third film structure,forming the second film structure including forming a lower siliconnitride film, forming a lower silicon oxide film on the lower siliconnitride film, forming an intermediate insulating film on the lowersilicon oxide film, the intermediate insulating film containing a metalelement and having a relative dielectric constant of greater than 7,forming an upper silicon oxide film on the intermediate insulating film,and forming an upper silicon nitride film on the upper silicon oxidefilm; forming the third film structure including forming a lower siliconnitride film, forming an intermediate insulating film on the lowersilicon nitride film, the intermediate insulating film containing ametal element and having a relative dielectric constant of greater than7, and forming an upper silicon nitride film on the intermediateinsulating film, forming the second insulating film including, afterforming the lower silicon nitride film, performing a heat treatment at atemperature higher than that at which the lower silicon nitride film isformed.
 16. A method for manufacturing a semiconductor device, themethod comprising: forming a first insulating film on a semiconductorsubstrate; forming a charge storage layer on the first insulating film;forming a second insulating film on the charge storage layer; andforming a control electrode film on the second insulating film, formingthe second insulating film including forming a silicon nitride film onthe charge storage layer, forming the silicon nitride film includingforming a silicon layer on the charge storage layer and nitriding thesilicon layer.